High solids tolerant invert emulsion fluids

ABSTRACT

A low gravity solid tolerant emulsifier and methods of making the same. The emulsifier includes a maleated amido-amine reaction product produced by: (1) reacting a fatty acid material comprising, and an amine material (e.g., a amine having a amine value of about 700 to about 1300 mg/g, such as AMINE HST) to produce an amido-amine reaction product; and (2) reacting the amido-amine reaction product with maleic anhydride to produce the maleated amido-amine reaction product. An invert emulsion fluids and drilling fluids that include the emulsifier of described herein and methods of using the same.

CROSS-REFERENCE TO RELATED APPLICATION

The present disclosure is a continuation of U.S. Non-Provisionalapplication Ser. No. 16/261,925, filed 30 Jan. 2019, titled HIGH SOLIDSTOLERANT INVERT EMULSION FLUIDS, which claims priority to U.S.Provisional Application Ser. No. 62/623,689, filed 30 Jan. 2018, thecontents of each are incorporated herein by reference in their entiretyfor all purposes.

FIELD

The present disclosure relates to an invert emulsion fluid compositionand associated methods. In particular, the disclosure provides reactionproducts of amine, low titer fatty acid material, and maleic anhydrideas emulsifiers for invert emulsion drilling fluids, and drilling fluidcompositions comprising the same. The invert emulsion fluids (IEF) isstable and has high tolerance for low gravity solids (LGS) providingcontrolled (low) rheology. The present disclosure also provides methodsof synthesizing an economic and effective drilling fluid composition foroil and gas drilling.

BACKGROUND

A drilling fluid is a specially designed fluid that is circulatedthrough an oil or gas wellbore as the wellbore is drilled to facilitatethe drilling operation. A need exists for an improved additive formodifying and controlling the suspension properties of drilling fluidsthat would be efficient, easily handled, and readily dispersible in abroad range of drilling muds, and usable under a broad range ofconditions.

Drilling fluids or muds are typically classified according to their basefluid or continuous phase, as water base and oil base fluids. Drillingfluids may contain a mixture of base fluids, and are typicallyclassified by the predominating or continuous base fluid, with the fluidpresent in lesser quantities becoming the internal or emulsified phase.The use of oil and invert oil-based drilling fluids or muds in oilexploration is increasing rapidly owing to the more demandingrequirements encountered in drilling deep and/or non-vertical anddeviated wells. Compared with the longer-established water-baseddrilling muds, oil and invert oil-based drilling fluids possess a numberof advantages, including reduced interaction with earth formations, andimproved lubricity. The drilling fluids and methods of the presentdisclosure are particularly useful in invert emulsion systems.

Oil based invert emulsion drilling fluids are generally used throughoutthe world and consist of a three-phase system: oil, internal hygroscopicphase and fine particulate solids. The internal hygroscopic phase can bean aqueous phase typically a brine or it can be an organic compound likeglycerol or polyglycerol either dissolved in water or neat or acombination thereof. The addition of brine reduces the overall price ofthe fluid, reduces the risk of combustion of the oil, builds an emulsionstructure that provides suspension and improved viscosity to the fluid,provides improved shale stability by driving water out of the shale andinto the fluid via osmosis, and improves the water acceptance of themud. The brine of choice is commonly an aqueous solution of an inorganicsalt, such as sodium chloride or calcium chloride.

Drilling fluids or drilling muds are pumped under pressure down througha long string of drill pipe, then through the center of the drilling bitat the hole bottom, then back up through the annulus between the outsideof the string of drill pipe and up the borehole wall to the surface.

Drilling fluids provide a number of interrelated functions to satisfythe requirements of the oil industry for a commercial drilling fluid,which may be grouped as follows. (1) The drilling fluid must suspend andtransport solid particles, e.g. drill cuttings, to the surface forscreening out and disposal. (2) The drilling fluid must build a filtercake that can prevent the loss of downhole pressure and fluid loss tothe formation, including when traversing an interval of porous formationmaterial. (3) The drilling fluid must keep suspended an additiveweighting agent (to increase specific gravity of the mud), so thatuniform mud weight is maintain throughout the column of drilling fluidin the well, especially when encountering pressurized pockets ofcombustible gas, which otherwise would tend to reduce downhole pressure,as well as creating a “blowout” in which the fluid and even the drillstem are violently ejected from the well, with resulting catastrophicdamages, such as fires. (4) The drilling fluid must constantly lubricatethe drill bit so as to promote drilling efficiency and retard bit wear.(5) The drilling fluid should maintain sufficient hydrostatic pressureto manage the wellbore pressure for improved wellbore stability.

It should be noted that a drilling fluid must perform its variousfunctions not only when the drill bit is actively encountering thebottom of the borehole, but also at times when the drill stem isinactive, or is being removed or re-inserted for some purpose. Inparticular, cuttings must be held in suspension in the event ofshut-downs in drilling.

An ideal drilling fluid is a thixotropic system. That is, the drillingfluid (1) will exhibit low viscosity when sheared, such as duringagitation or circulation (as by pumping or otherwise) but, (2) when theshearing action is halted, the fluid must gel to hold the cuttings inplace, and it must become gelled relatively rapidly, reaching asufficient gel strength before suspended materials fall any significantdistance, and (3) this behavior should be almost completely reversible.In addition, even when it is a free-flowing liquid, the fluid mustretain a sufficiently high viscosity to carry all unwanted particulatematter from the bottom of the hole to the surface. Moreover, uponlong-term interruption of circulation, such as when drilling fluid hasbeen ejected from the borehole into a quiescent holding vessel or pond,the gel structure should remain intact to allow the weighting agentparticles to remain suspended and maintain a uniform distributionthroughout the fluid.

During the drilling process, some of the drilled solids erode and becomefiner particles that cannot be removed via solids control equipment (atthe surface) due to their small size. As drilling progresses theseparticles become finer to colloidal size and increase in theirconcentration in the drilling fluid. These colloidal fines and theirconcentration can negatively impact the performance of the invertemulsion fluid (IEF). The performance of the IEF can be gauged by theAmerican Petroleum Institute (API) fluid loss test, rheology andmonitoring for emulsion stability. These colloidal fines can eithercause an increase in the API fluid loss, increase the overall rheologyof the fluids or at the very end may even destabilize the IEF. Thisincrease in the overall rheology of the fluid can be determined by anincrease in Fann 35 rheometer readings from 600 rotations per minute(rpm) to 3 rpm. An increase in overall rheology of the fluid increasesthe equivalent circulating density (ECD) of the fluid. The ECD is theeffective density of the circulating fluid in the wellbore resultingfrom the sum of the hydrostatic pressure imposed by the static fluidcolumn and the friction pressure. API STD 65—Part 2, Isolating PotentialFlow Zones During Well Construction, Upstream Segment, Second Edition,December 2010. Global Standards. More specifically, an increase in therheology increases the frictional pressure component in the ECDequation, and thereby, the ECD of the fluid. The ECD is an importantparameter in avoiding kicks and losses of the fluid, particularly inwells that have a narrow window between the fracture gradient andpore-pressure gradient.

When the colloidal fines in the IEF increase, the fluid may be treatedin one or more of the following ways, for example, by: (i) adding athinner to lower the rheology; (ii) adding wetting agents to maintainthe water wettability of the colloidal fines; (iii) adding fresh IEF todilute the overall drilling fluid to reduce the overall concentration ofthe low gravity solids (LGS); (iv) performing high speed centrifugeoperations to remove the finer solids; and/or (v) adding other additivesto maintain a workable fluid. However, at times these treatments may notwork and the whole of the used IEF has to be discarded and fresh IEFmade.

It is therefore advantageous to have emulsifiers or additives as part ofthe IEF that reduce the maintenance/treatments of these fluids bymaintaining controlled (low) rheology profile and API fluid lossperformance of the IEF. This improvement will in turn increase theoverall working longevity of the IEF. Thus, there is a need for a costeffective drilling fluid that can perform all the above mentionedfunctions. The present disclosure provides a drilling fluid with an IEFcomposition having low titer low titer fatty acid material (or low titerrosin acid containing fatty acid material) based specialty emulsifierwhich delivers a low rheology IEF even in the presence of a highconcentration of low gravity solids (LGS). A low rheology in turn leadsto lower induced fluid losses in the drilling fluid formation whendrilling oil and gas wells.

SUMMARY

The present disclosure provides a low gravity solids (LGS) tolerantemulsifier, maleated low titer fatty acid material, or low titer rosincontaining fatty acid material based amido-amine (herein, “MDTA”)emulsifier, an invert emulsion fluid (herein, “IEF”) comprising the MDTAemulsifier (i.e., the LGS tolerant emulsifier) of the presentdisclosure, drilling fluids comprising the IEF of the presentdisclosure, and associated methods of use. Surprisingly andunexpectedly, when incorporated into IEF compositions, the emulsifier ofthe present disclosure reduces IEF rheology even in the presence of ahigh LGS concentration—i.e. the IEF has a lower rheology as compared toan IEF without the MDTA emulsifier of the present disclosure. The lowrheology in turn leads to lower induced fluid losses in the drillingfluid formation when drilling oil and gas wells.

Thus, in an aspect, the present disclosure provides a LGS tolerantemulsifier or MDTA emulsifier comprising a maleated amido-amine reactionproduct. The maleated amido-amine reaction product can be produced by:reacting a low titer fatty acid material (e.g., a lower titer fatty acidmaterial comprising rosin acid) and an amine material to produce anamido-amine reaction product (or amido-amine intermediate reactionproduct or amido-amine low-titer fatty acid material intermediatereaction product or amido-amine low-titer rosin acid containing fattyacid material intermediate reaction product), and reacting theamido-amine reaction product with maleic anhydride to produce themaleated amido-amine reaction product.

In another aspect, the present disclosure provides methods forpreparing/making a LGS tolerant emulsifier or a MDTA emulsifier. Themethod comprises: reacting a low titer fatty acid material (i.e., a lowtiter fatty acid material comprising rosin acid) and an amine materialto produce an amido-amine low-titer fatty acid material intermediate (oramido-amine reaction product or amido-amine intermediate reactionproduct); and reacting the amido-amine low-titer fatty acid materialintermediate or reaction product with maleic anhydride (e.g., addingmaleic anhydride) to produce a maleated amido-amine reaction product orMDTA emulsifier. In certain embodiments, the method of preparing a MDTAemulsifier comprises reacting low titer fatty acid material (i.e., lowtiter rosin acid containing fatty acid material) and an amine resultingin an amido-amine-low titer fatty acid material intermediate; andreacting the intermediate with maleic anhydride (i.e., maleic anhydrideaddition) to form the LGS tolerant emulsifier or MDTA emulsifier.

In any aspect or embodiment described herein, the LGS tolerantemulsifier or MDTA emulsifier includes at least one of: the low titerfatty acid material or low titer rosin acid containing fatty acidmaterial is present in an amount of about 55 wt. % to about 95 wt. %(e.g., about 65 wt. % to about 75 wt. %) of the amido-amine reactionproduct; the amine material is present in an amount of about 5 wt. % toabout 45 wt. % (e.g., about 25 wt. % to about 35 wt. %) of theamido-amine reaction product; the maleic anhydride is present in anamount of about 1 wt. % to about 20 wt. % (e.g., about 5 wt. % to about13 wt. %) of the maleated amido-amine reaction product or theemulsifier; or a combination thereof.

In any of the aspects or embodiments described herein, the low titerfatty acid material (e.g., low titer fatty material comprising rosinacid or low titer rosin acid containing material) includes or is atleast one of: a side stream from the crude tall oil (CTO) refiningprocess collected as the bottoms product during the subsequentproduction of low rosin (<5%) and low Gardner Color index (<7.0) talloil fatty acid (TOFA) from refinery columns during the distillation ofcrude tall oil (CTO); a mixture of a blend of the side stream and atleast one of distilled tall oil, tall oil fatty acid, rosin, or acombination thereof; a product stream of the CTO refining process; amixture or blend of TOFA and distilled tall oil; a mixture or blend of adistilled tall oil and rosin; a mixture or blend of TOFA and rosin; adisproportionated tall oil, a mixture of disproportionated tall oil androsin, a mixture of disproportionated tall oil and TOFA, a mixture ofdisproportionated tall oil and distilled tall oil (DTO), or acombination thereof; or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acidmaterial or low titer fatty acid material comprising rosin acid has atleast one of: an acid number ranging from about 143 to about 200 mg/g; arosin acid concentration of about 11% to about 50%; a titer point ofless than about 14° C.; a PAN rosin acid concentration of less than orequal to about 50%; heavies present in an amount of less than or equalto about 40% of the low titer fatty acid material; a Gardner color indexin a range from about 4.0 to about 17.0; or a combination thereof. Forexample, in certain embodiments, the low titer fatty acid material hasan acid number in a range from about 155 to about 174 mg/g or about 143to about 185 mg/g. In any aspect or embodiment described herein, the lowtiter fatty acid material has a Gardner color index in a range from 4 toabout 14.7.

In any of the aspects or embodiments described herein, the amine HST hasan amine value between about 700 mg/g and about 1300 mg/g (e.g., about750 mg/g to about 900 mg/g or about 750 mg/g).

In any aspect or embodiment described herein, the amine materialincludes or is a distillation residuum bottom composition of a reactionproduct of monoethanolamine and ammonia in which piperazine distillateproduct has been recovered.

In any of the aspects or embodiments described herein, the aminematerial includes or is a chemical composition with the ChemicalAbstracts Service Registry No. 68910-05-4. For example, in certainembodiments, the amine material is or includes at least one of AMINE HSTfrom Dow Chemical Co. (Midland, Mich.), AMIX 1000 from BASF(Ludwigshafen, Germany), Berolamine 20 (BA-20; AkzoNobel, IllinoisChicago), or a combination thereof.

In particular embodiments, the amine material includes or is adistillation residuum bottom composition of a reaction product ofmonoethanolamine and ammonia in which piperazine distillate product hasbeen recovered.

In any aspect or embodiment described herein, the amine materialincludes at least one of: diethylenetriamine (DETA),hydroxyethyldiethylenetriamine (HEDETA), 2-piperazinoethanol,triethylenetetramine (TETA), Tetraethylenepentamine mixtures (TEPA),pentaethylene hexamine (PEHA) heptaethyleneoctamine (HEOA),hexaethyleneheptamine (HEHA), amine HST, amine DCT, aminoethylpiperazine(AEP), dimethylaminopropylamine (DMAPA), aminoethylethanolamine (AEEA),diethanolamine (DEA), triethanolamine (TEA), monoethanolamine, otherhigher ethylene amines, or combinations thereof.

In an embodiment, the amine material is or includes a chemicalcomposition with the Chemical Abstract Service Registry No. 68910-05-4(e.g., AMINE HST from Dow Chemical Co., AMIX 1000 from BASF, BA-20 fromAkzo Nobel, or a combination thereof).

In certain embodiments, the amine material includes at least one of:AMINE HST from Dow Chemical Co., AMIX 1000 from BASF, BA-20 from AkzoNobel, or a combination thereof.

In any aspect or embodiment described herein, the amido-amine reactionproduct (i.e., the amido-amine reaction intermediate product oramido-amine low-titer fatty acid material intermediate reaction product)includes at least one of amidoamines, alkanolamides, di-amidoamine,di-ester alcohol amine, ester alcohol amine, di-ester amine, ester amidoamines, amido amine alcohols, amides of the hydroxy piperazine, amideimidazoline, ester imidazoline, amine imidazoline, alkanol imidazolineor combinations thereof.

In an additional aspect, the present disclosure provides an invertemulsion fluid (IEF) comprising the LGS tolerant emulsifier or MDTAemulsifier of the present disclosure, and at least one of a non-aqueouscontinuous phase, a discontinuous hygroscopic phase like brine, anadditive, or a combination thereof. The IEF of the present disclosure,which includes the LGS tolerant emulsifier or MDTA emulsifier of thepresent disclosure, demonstrates controlled (i.e., reduced) rheologyeven in the presence of relatively high concentration of LGS, ascompared to a maleated TOFA amido-amine (herein, “MHTA”) emulsifier,which is generally recognized as the industry standard. See, forexample, an emulsifier as disclosed in U.S. Pat. No. 8,927,468 B2, whichis incorporated herein, as well as non-spray dried version thereof.

In any aspect or embodiment described herein, the IEF comprises betweenabout 4 and about 12 V/V of LGS. In any aspect or embodiment describedherein, the LGS have specific gravity between about 2.0 and about 3.0.

In any aspect or embodiment described herein, the IEF of the presentdisclosure has a low high temperature, high pressure (HTHP) fluid lossbetween about 1 and about 20 ml at 350° F. See, American PetroleumInstitute (API) Recommended Practice 13B-2, Fourth Edition, RecommendedPractice for Field Testing of Oil-based Drilling Fluids, for anexemplary test method to conduct the HTHP filtration test at the testtemperature indicated above.

In any aspect or embodiment described herein, the IEF has a lowerrheology than an IEF without the MDTA emulsifier (e.g., an IEFcomprising a maleated TOFA amido-amine emulsifier).

In any aspect or embodiment described herein, the MDTA emulsifier of thepresent disclosure reduces the IEF rheology by from about 10 to about92% (e.g., about 25 to about 85% or about 50 to about 85%), as comparedto an IEF comprising a MHTA emulsifier (i.e., the industry standard). Inany aspect or embodiment described herein, the IEF of the presentdisclosure has a low rheology having 600 rpm to 3 rpm dial readings thatare lower than similarly formulated IEF with a MHTA emulsifiers at 150°F. In any aspect or embodiment described herein, the relative rheologymay be determined at 100 ppb loading REVDUST® tested under standardconditions (e.g., an exemplary test method/conditions can be found atAPI Recommended Practice 13B-2, Fourth Edition, Recommended Practice forField Testing of Oil-based Drilling Fluids).

In any aspect or embodiment described herein, the IEF of the presentdisclosure has a gel strength that is about 10 to about 92% (e.g., about25 to about 85% or about 50 to about 85%) lower than a similarlyformulated IEF without the described MDTA emulsifier (e.g., a similarlyformulated IEF with a maleated TOFA amine emulsifier) at 150° F. In anyaspect or embodiment described herein, the gel strength may bedetermined by API Recommended Practice 13B-2, Fourth Edition,Recommended Practice for Field Testing of Oil-based Drilling Fluids.

In any aspect or embodiment described herein, the IEF of the presentdisclosure has a low rheology having yield stress (Tau0) less than theyield stress of similarly formulated IEF without the described MDTAemulsifier (e.g., a similarly formulated IEF comprising a MHTAemulsifier) at 150° F.

In any aspect or embodiment described herein, the IEF of the presentdisclosure is used for gas and oil drilling.

In a further aspect, the present disclosure provides a drilling fluidcomprising the IEF of the present disclosure (i.e., an IEF comprisingthe MDTA emulsifier of the present disclosure).

A further aspect of the present disclosure provides a method of drillinga well. The method comprises drilling a well bore and circulating thedrilling fluid of the present disclosure through said well bore whendrilling the well bore.

Further aspects, features, and advantages of the present disclosure willbe apparent to those of ordinary skill in the art upon examining andreading the following Detailed Description of the Preferred Embodiments.

BRIEF DESCRIPTION OF THE FIGURES

The accompanying drawings, which are incorporated into and form a partof the specification, illustrate several embodiments of the presentinvention and, together with the description, serve to explain theprinciples of the invention. The drawings are only for the purpose ofillustrating an embodiment of the invention and are not to be construedas limiting the invention. Further objects, features and advantages ofthe invention will become apparent from the following detaileddescription taken in conjunction with the accompanying figures showingillustrative embodiments of the invention, in which:

FIG. 1 is a graph illustrating shear stress relative to shear rate ofexemplary solids tolerant emulsifiers and maleated TOFA amido-amineemulsifier.

FIG. 2 is a graph illustrating shear stress relative to shear rate ofexemplary solids tolerant emulsifiers and a second maleated TOFAamido-amine emulsifier.

DETAILED DESCRIPTION

The following is a detailed description provided to aid those skilled inthe art in practicing the present disclosure. Those of ordinary skill inthe art may make modifications and variations in the embodimentsdescribed herein without departing from the spirit or scope of thepresent disclosure. All publications, patent applications, patents,figures and other references mentioned herein are expressly incorporatedherein by reference in their entirety for all purposes.

The present description provides improved compositions and methods fordrilling wells, fracturing subterranean formations, and othertreatments. The drilling and fracturing compositions and methods of thepresent disclosure are economical and desirable properties that aresurprising and unexpected. In particular, the present disclosureprovides a low gravity solids (LGS) tolerant emulsifier or maleated lowtiter fatty acid material (also referred to herein as a low titer fattyacid material comprising rosin acid or a low titer rosin acid containingfatty acid material) based amido-amine (herein, “MDTA”) emulsifier,invert emulsion fluid (herein, “IEF”) comprising the LGS tolerantemulsifier or MDTA emulsifier of the present disclosure, drilling fluidscomprising the IEF of the present disclosure, and associated methods ofuse of each. Surprisingly and unexpectedly, when the LGS tolerantemulsifier or MDTA emulsifier of the present disclosure is incorporatedinto IEF compositions, the rheology of the IEF is reduced, even in thepresence of a high LGS concentration—i.e. the IEF of the presentdisclosure has a lower rheology as compared to an IEF formulated with aconventional MHTA emulsifier (i.e., without the emulsifier of thepresent disclosure). The low rheology in turn leads to lower inducedfluid losses in the drilling fluid formation when drilling oil and gaswells

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure belongs. The terminology used in thedescription is for describing particular embodiments only and is notintended to be limiting of the disclosure.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise (such as in the case of a groupcontaining a number of carbon atoms in which case each carbon atomnumber falling within the range is provided), between the upper andlower limit of that range and any other stated or intervening value inthat stated range is encompassed within the disclosure. The upper andlower limits of these smaller ranges may independently be included inthe smaller ranges is also encompassed within the disclosure, subject toany specifically excluded limit in the stated range. Where the statedrange includes one or both of the limits, ranges excluding either bothof those included limits are also included in the disclosure.

The following terms are used to describe the present disclosure. Unlessotherwise defined, all technical and scientific terms used herein havethe same meaning as commonly understood by one of ordinary skill in theart to which this disclosure belongs. The terminology used in thedescription is for describing particular embodiments only and is notintended to be limiting of the disclosure.

The articles “a” and “an” as used herein and in the appended claims areused herein to refer to one or to more than one (i.e., to at least one)of the grammatical object of the article unless the context clearlyindicates otherwise. By way of example, “an element” means one elementor more than one element.

The phrase “and/or,” as used herein in the specification and in theclaims, should be understood to mean “either or both” of the elements soconjoined, i.e., elements that are conjunctively present in some casesand disjunctively present in other cases. Multiple elements listed with“and/or” should be construed in the same fashion, i.e., “one or more” ofthe elements so conjoined. Other elements may optionally be presentother than the elements specifically identified by the “and/or” clause,whether related or unrelated to those elements specifically identified.Thus, as a non-limiting example, a reference to “A and/or B”, when usedin conjunction with open-ended language such as “comprising” can refer,in one embodiment, to A only (optionally including elements other thanB); in another embodiment, to B only (optionally including elementsother than A); in yet another embodiment, to both A and B (optionallyincluding other elements); etc.

As used herein in the specification and in the claims, “or” should beunderstood to have the same meaning as “and/or” as defined above. Forexample, when separating items in a list, “or” or “and/or” shall beinterpreted as being inclusive, i.e., the inclusion of at least one, butalso including more than one, of a number or list of elements, and,optionally, additional unlisted items. Only terms clearly indicated tothe contrary, such as “only one of” or “exactly one of,” or, when usedin the claims, “consisting of,” will refer to the inclusion of exactlyone element of a number or list of elements. In general, the term “or”as used herein shall only be interpreted as indicating exclusivealternatives (i.e., “one or the other but not both”) when preceded byterms of exclusivity, such as “either,” “one of,” “only one of,” or“exactly one of.”

In the claims, as well as in the specification above, all transitionalphrases such as “comprising,” “including,” “carrying,” “having,”“containing,” “involving,” “holding,” “composed of,” and the like are tobe understood to be open-ended, i.e., to mean including but not limitedto. Only the transitional phrases “consisting of” and “consistingessentially of” shall be closed or semi-closed transitional phrases,respectively, as set forth in the United States Patent Office Manual ofPatent Examining Procedures, Section 2111.03.

As used herein in the specification and in the claims, the phrase “atleast one,” in reference to a list of one or more elements, should beunderstood to mean at least one element selected from anyone or more ofthe elements in the list of elements, but not necessarily including atleast one of each and every element specifically listed within the listof elements and not excluding any combinations of elements in the listof elements. This definition also allows that elements may optionally bepresent other than the elements specifically identified within the listof elements to which the phrase “at least one” refers, whether relatedor unrelated to those elements specifically identified. Thus, as anon-limiting example, “at least one of A and B” (or, equivalently, “atleast one of A or B,” or, equivalently “at least one of A and/or B”) canrefer, in one embodiment, to at least one, optionally including morethan one, A, with no B present (and optionally including elements otherthan B); in another embodiment, to at least one, optionally includingmore than one, B, with no A present (and optionally including elementsother than A); in yet another embodiment, to at least one, optionallyincluding more than one, A, and at least one, optionally including morethan one, B (and optionally including other elements); etc.

It should also be understood that, in certain methods described hereinthat include more than one step or act, the order of the steps or actsof the method is not necessarily limited to the order in which the stepsor acts of the method are recited unless the context indicatesotherwise.

As used herein, the term “drilling” or “drilling well bores” shall beunderstood in the broader sense of drilling operations, which includerunning casing and cementing as well as drilling, unless specificallyindicated otherwise. The present disclosure also provides invertemulsion based drilling fluids for use in the methods of the disclosureto effect the advantages of the disclosure.

The present disclosure provides an invert emulsion drilling fluid thatmeets environmental constraints and provides improved performance in thefield.

As disclosed herein, a “gel” may be defined a number of ways. Onedefinition indicates that a “gel” is a generally colloidal suspension ora mixture of microscopic water particles (and any hydrophilic additives)approximately uniformly dispersed through the oil (and any hydrophobicadditives), such that the fluid or gel has a generally homogeneousgelatinous consistency. Another definition states that a “gel” is acolloid in a more solid form than a “sol”, which is a fluid colloidalsystem, especially one in which the continuous phase is a liquid. Stillanother definition provides that a “gel” is a colloid in which thedisperse phase has combined with the continuous phase to produce aviscous jelly-like product. Generally, a gel has a structure that iscontinually building. If the yield stress of a fluid increases overtime, the fluid has gelled. “Yield stress” is the stress required to beexerted to initiate deformation.

During drilling, the fluids of the present disclosure generally maintainconsistently low values for the difference in their surface density anddownhole equivalent circulating density (ECD), as well as havesignificantly reduced fluid loss, as compared to other (e.g.,conventional) drilling fluids used under comparable conditions.

Oil or synthetic fluid-based muds are normally used to drill swelling orsloughing shales, salt, gypsum, anhydrite or other evaporate formations,hydrogen sulfide-containing formations, and hot boreholes (e.g. greaterthan about 300° F.) holes, but may be used in other holes penetrating asubterranean formation as well. Unless indicated otherwise, the terms“oil mud” or “oil-based mud or drilling fluid” shall be understood toinclude synthetic oils or other synthetic fluids as well as natural ortraditional oils, and such oils shall be understood to comprise invertemulsions.

Oil-based muds used in drilling typically comprise: a base oil (e.g.natural or synthetic fluid) comprising the external phase of an invertemulsion; a saline, aqueous solution (e.g. an aqueous solutioncomprising about 20 to about 40% calcium chloride, or about 25% to about35% calcium chloride, or about 30% calcium chloride) comprising theinternal phase of the invert emulsion; emulsifiers at the interface ofthe internal and external phases; and other agents or additives forsuspension, weight or density, oil-wetting, fluid loss or filtrationcontrol, and rheology control. Such additives commonly includeorganophilic clays and organophilic lignites. See H. C. H. Darley andGeorge R. Gray, Composition and Properties of Drilling and CompletionFluids 66-67, 561-562 (5th ed. 1988). In any aspect or embodimentdescribed herein, the oil-based or invert emulsion-based drilling fluidcomprises between about 50:50 to about 95:5 by volume oil phase to waterphase. In some embodiments, the drilling fluid is a completely oil mudsimply comprises 100% liquid phase oil by volume; that is, there is noaqueous internal phase.

Invert emulsion drilling fluids (also called invert drilling muds orinvert muds or fluids) comprise a key segment of the drilling fluidsindustry. However, increasingly invert emulsion-based drilling fluidshave been subjected to greater environmental restrictions, as well asperformance and cost demands. There is consequently an increasing needand industry-wide interest in new drilling fluids that provide improvedperformance while still affording environmental and economicalacceptance. Furthermore, the automotive and metalworking industries arealways looking for low cost, highly efficient lubricants and lubricantadditives that are environmentally friendly and that have a high thermalstability. Many lubricants and lubricant additives currently used, e.g.,in these industries, do not meet these performance criteria. Inaddition, most of them are petroleum-based and thus, non-renewable.

The compositions of the present disclosure relate to drilling fluidadditives (e.g., a LGS tolerant emulsifier or MDTA emulsifier) anddrilling fluids, which are also known as drilling muds in the oilservice industry, that have surprising and unexpected improvements inlow gravity solids tolerance, while maintaining controlled (low)rheology. In particular, the compositions of the present disclosurerelate to oil and invert oil based emulsion types of drilling fluids inwhich water is dispersed in an oil-based medium. Such drilling fluidcompositions when prepared at a mud plant are often called mud plantformulations. The disclosure is particularly directed to providing aninvert emulsion fluid with low rheology and that is tolerant to highconcentrations of low gravity solids.

Maleated Low Titer Fatty Acid Material Based Amine Emulsifier

An aspect of the present disclosure provides a low gravity solid (LGS)tolerant emulsifier or MDTA emulsifier. The emulsifier of the presentdisclosure includes a maleated amido-amine reaction product produced byreacting a low titer fatty acid material (e.g., a low titer fatty acidmaterial comprising rosin acid or low titer rosin acid containing fattyacid material) with an amine material to produce an amido-aminelow-titer fatty acid material intermediate reaction product (oramido-amine intermediate product or amido-amine reaction product), andreacting the amido-amine low-titer fatty acid material intermediatereaction product with maleic anhydride to produce the maleatedamido-amine reaction product. The reaction conditions like temperatureand hold time at the highest temperature are specially engineered toderive maximum LGS tolerance. As used herein, unless the contextindicates otherwise, the term low titer fatty acid material amido-amineis used inclusively of bis-amide amine, amido amines, alkanol amides,ester amido amines, amido amine alcohols, amides of the hydroxypiperazine, produced according to the methods described herein from thereaction of a low titer fatty acid material with an amine source.

In any aspect or embodiment described herein, the low titer fatty acidmaterial or low titer rosin acid containing fatty acid materialcomprises about 55 wt. % to about 95 wt. % of the amido-amine reactionproduct. For example, in certain embodiments, the low-titer fatty acidmaterial is present in an amount of about 55 wt. % to about 95 wt. %,about 55 wt. % to about 90 wt. %, about 55 wt. % to about 85 wt. %,about 55 wt. % to about 80 wt. %, about 55 wt. % to about 75 wt. %,about 55 wt. % to about 70 wt. %, about 55 wt. % to about 65 wt. %,about 55 wt. % to about 60 wt. %, about 60 wt. % to about 95 wt. %,about 60 wt. % to about 90 wt. %, about 60 wt. % to about 85 wt. %,about 60 wt. % to about 80 wt. %, about 60 wt. % to about 75 wt. %,about 60 wt. % to about 70 wt. %, about 60 wt. % to about 65 wt. %,about 65 wt. % to about 95 wt. %, about 65 wt. % to about 90 wt. %,about 65 wt. % to about 85 wt. %, about 65 wt. % to about 80 wt. %,about 65 wt. % to about 75 wt. %, about 65 wt. % to about 70 wt. %,about 70 wt. % to about 95 wt. %, about 70 wt. % to about 90 wt. %,about 70 wt. % to about 85 wt. %, about 70 wt. % to about 80 wt. %,about 70 wt. % to about 75 wt. %, about 75 wt. % to about 95 wt. %,about 75 wt. % to about 90 wt. %, about 75 wt. % to about 85 wt. %,about 75 wt. % to about 80 wt. %, about 80 wt. % to about 95 wt. %,about 80 wt. % to about 90 wt. %, about 80 wt. % to about 85 wt. %,about 85 wt. % to about 95 wt. %, about 85 wt. % to about 90 wt. %, orabout 90 wt. % to about 95 wt. %, of the amido-amine reaction product.In any aspect or embodiment described herein, the low titer fatty acidmaterial or low titer rosin acid containing fatty acid material ispresent in an amount of about 55 wt. %, about 56 wt. %, about 57 wt. %,about 58 wt. %, about 59 wt. %, about 60 wt. %, about 61 wt. %, about 62wt. %, about 63 wt. %, about 64 wt. %, about 65 wt. %, about 66 wt. %,about 67 wt. %, about 68 wt. %, about 69 wt. %, about 70 wt. %, about 71wt. %, about 72 wt. %, about 73 wt. %, about 74 wt. %, about 75 wt. %,about 76 wt. %, about 77 wt. %, about 78 wt. %, about 79 wt. %, about 80wt. %, about 81 wt. %, about 82 wt. %, about 83 wt. %, about 84 wt. %,about 85 wt. %, about 86 wt. %, about 87 wt. %, about 88 wt. %, about 89wt. %, about 90 wt. %, about 91 wt. %, about 92 wt. %, about 93 wt. %,about 94 wt. %, or about 95 wt. % of the amido-amine reaction product.

In any aspect or embodiment described herein, the amine material (ormixture of amines) is present in an amount of about 5 wt. % to about 45wt. % of the amido-amine reaction product. For example, in certainembodiments, the amine or amines is/are present in an amount of about 5wt. % to about 45 wt. %, about 5 wt. % to about 40 wt. %, about 5 wt. %to about 35 wt. %, about 5 wt. % to about 30 wt. %, about 5 wt. % toabout 25 wt. %, about 5 wt. % to about 20 wt. %, about 5 wt. % to about15 wt. %, about 10 wt. % to about 45 wt. %, about 10 wt. % to about 40wt. %, about 10 wt. % to about 35 wt. %, about 10 wt. % to about 30 wt.%, about 10 wt. % to about 25 wt. %, about 10 wt. % to about 20 wt. %,about 15 wt. % to about 45 wt. %, about 15 wt. % to about 40 wt. %,about 15 wt. % to about 35 wt. %, about 15 wt. % to about 30 wt. %,about 15 wt. % to about 25 wt. %, about 20 wt. % to about 45 wt. %,about 20 wt. % to about 40 wt. %, about 20 wt. % to about 35 wt. %,about 20 wt. % to about 30 wt. %, about 25 wt. % to about 45 wt. %,about 25 wt. % to about 40 wt. %, about 25 wt. % to about 35 wt. %,about 30 wt. % to about 45 wt. %, about 30 wt. % to about 40 wt. %, orabout 35 wt. % to about 45 wt. % of the amido-amine reaction product. Inany aspect or embodiments described herein, the amine or combination ofamines is present in an amount of about 5 wt. %, 6 wt. %, 7 wt. %, 8 wt.%, 9 wt. %, 10 wt. %, 11 wt. %, 12 wt. %, 13 wt. %, 14 wt. %, 15 wt. %,16 wt. %, 17 wt. %, 18 wt. %, 19 wt. %, 20 wt. %, 21 wt. %, 22 wt. %, 23wt. %, 24 wt. %, about 25 wt. %, about 26 wt. %, about 27 wt. %, about27 wt. %, about 28 wt. %, about 29 wt. %, about 30 wt. %, about 31 wt.%, about 32 wt. %, about 33 wt. %, about 34 wt. %, about 35 wt. %, about36 wt. %, about 37 wt. %, about 38 wt. %, about 39 wt. %, about 40 wt.%, about 41 wt. %, about 42 wt. %, about 43 wt. %, about 44 wt. %, orabout 45 wt. % of the amido-amine reaction product.

In any aspect or embodiment described herein, the maleic anhydridecomprises about 1 wt. % to about 20 wt. % of the maleated amido-aminoreaction product or the emulsifier composition. For example, in certainembodiments, the maleic anhydride is present in an amount of about 1 wt.% to about 20 wt. %, about 2.5 wt. % to about 20 wt. %, about 5 wt. % toabout 20 wt. %, about 7.5 wt. % to about 20 wt. %, about 10 wt. % toabout 20 wt. %, about 12.5 wt. % to about 20 wt. %, about 15 wt. % toabout 20 wt. %, about 17.5 wt. % to about 20 wt. %, about 1 wt. % toabout 17.5 wt. %, about 2.5 wt. % to about 17.5 wt. %, about 5 wt. % toabout 17.5 wt. %, about 7.5 wt. % to about 17.5 wt. %, about 10 wt. % toabout 17.5 wt. %, about 12.5 wt. % to about 17.5 wt. %, about 15 wt. %to about 17.5 wt. %, about 1 wt. % to about 15 wt. %, about 2.5 wt. % toabout 15 wt. %, about 5 wt. % to about 15 wt. %, about 7.5 wt. % toabout 15 wt. %, about 10 wt. % to about 15 wt. %, about 12.5 wt. % toabout 15 wt. %, about 1 wt. % to about 15 wt. %, about 2.5 wt. % toabout 15 wt. %, about 5 wt. % to about 15 wt. %, about 7.5 wt. % toabout 15 wt. %, about 10 wt. % to about 15 wt. %, about 12.5 wt. % toabout 15 wt. %, about 1 wt. % to about 12.5 wt. %, about 2.5 wt. % toabout 12.5 wt. %, about 5 wt. % to about 12.5 wt. %, about 7.5 wt. % toabout 12.5 wt. %, about 10 wt. % to about 12.5 wt. %, about 1 wt. % toabout 10 wt. %, about 2.5 wt. % to about 10 wt. %, about 5 wt. % toabout 10 wt. %, about 7.5 wt. % to about 10 wt. %, about 1 wt. % toabout 7.5 wt. %, about 2.5 wt. % to about 7.5 wt. %, about 5 wt. % toabout 7.5 wt. %, about 1 wt. % to about 5 wt. %, about 2.5 wt. % toabout 5 wt. %, or about 2.5 wt. % to about 5 wt. % of the maleatedamido-amine reaction product or the emulsifier composition. In anyaspect or embodiment described herein, the maleic anhydride is presentin an amount of about 1 wt. %, about 2 wt. %, about 3 wt. %, about 4 wt.%, about 5 wt. %, about 6 wt. %, about 7 wt. %, about 8 wt. %, about 9wt. %, about 10 wt. %, about 11 wt. %, about 12 wt. %, about 12 wt. %,about 13 wt. %, about 14 wt. %, about 16 wt. %, about 17 wt. %, about 18wt. %, about 19 wt. %, or about 20 wt. % of the maleated amido-aminereaction product or the emulsifier composition.

Low Titer Fatty Acid Material

In any aspects or embodiment described herein, the low titer fatty acidmaterial, low titer fatty acid material comprising rosin acid, or lowtiter rosin acid containing fatty acid material includes or is a sidestream from the crude tall oil (CTO) refining process. For example, thelow titer fatty acid material includes or is a side stream collected asthe bottoms product during the subsequent production of low rosin (<5%)and low Gardner Color index (<7.0) tall oil fatty acid (TOFA) fromrefinery columns during the distillation of crude tall oil (CTO). Forexample, in any aspect or embodiment described herein, the side streamfrom the CTO refining process is C2-B° (available from Ingevity,Charleston, S.C.). Thus, in any aspect or embodiment described herein,the low titer fatty acid material is or includes a side stream from theCTO refining process that has at least one of: an acid number of about143 mg/g to about 185 mg/g (e.g., about 155 mg/g to about 174 mg/g) orabout 150 mg/g to about 200 mg/g, about 12% to about 40% rosin acids, atiter point of less than −2° C., about 45% fatty acids, about 14%monounsaturated fatty acids, about 34% unsaturated fatty acids, lessthan about 3% saturated fatty acids, or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acidmaterial is or includes the side stream from the CTO refining processand at least one of distilled tall oil, tall oil fatty acid, rosin, or acombination thereof, wherein the rosin acid content of the low titerfatty acid material is as described herein.

In any aspect or embodiment described herein, the low titer fatty acidmaterial is or includes a product stream of the CTO refining process,wherein the CTO refining process product stream has a rosin acid contentas described herein. For example, in any aspect or embodiment describedherein, the CTO refining process product stream is (1) Altapyne™ M-28B(e.g., about 26 to about 30% or about 28% rosin acid content) (IngevityCorp., Charleston, S.C.); (2) a distilled tall oil having at least oneof about 11% to about 12% rosin acid, an acid number of less than orequal to about 188 mg/g, a Gardner Color Index of less than or equal toabout 8, less than or equal to about 1% palmitic acid, a titer point ofless than about 14° C., or a combination thereof; or (3) a combinationthereof. Thus, in any aspect or embodiment described herein, the lowtiter fatty acid material is or includes (1) a distilled tall oil havingat least one of: about 26% to about 30% rosin acid, an acid number of atleast about 180 mg/g, a Gardner Color Index of less than or equal to 10,a titer point of about 10° C. to about 12° C. (e.g., about 11° C.), or acombination thereof; (2) a distilled tall oil having at least one ofabout 11% to about 12% rosin acid, an acid number of less than or equalto about 188 mg/g, a Gardner Color Index of less than or equal to about8, less than or equal to about 1% palmitic acid, a titer point of lessthan about 14° C., or a combination thereof; or (3) a combinationthereof.

In any aspect or embodiment described herein, the low titer fatty acidmaterial is or includes one or more distilled tall oils (e.g., 1, 2, 3,4, 5, 6, or more distilled tall oils). For example, in any aspect orembodiment described herein, the distilled tall oil is or includes atleast one of: Altapyne™ M-50B (about 45.0 to about 48.5% rosin acidcontent), Altapyne™ M-25 (about 12.0 to about 40.0% rosin acid content),Altapyne™ M-38 (about 37.0 to about 43.0% rosin acid content), Altapyne™M-226 (about 25.0 to about 28.0% rosin acid content), or a combinationthereof. Thus, in any aspect or embodiment described herein, the lowtiter fatty acid material is or includes a distilled tall oil having atleast one of an acid number of about 175 mg/g to about 180 mg/g, about45 to about 48.5% rosin acid, a Gardner Color Index of no greater thanabout 17 (e.g., about 17), or a combination thereof. In any aspect orembodiment described herein, the low titer fatty acid material is orincludes a distilled tall oil having at least one of: an acid number ofabout 150 mg/g to about 200 mg/g, about 12.0 to about 40.0% rosin acid(e.g., about 20% rosin acid), a Gardner Color Index of about 10 to about12 (e.g., about 11), a titer point of less than or equal to −2° C.,about 45% fatty acids, less than about 3% saturated fatty acids, about14% monosaturated fatty acids, about 34% unsaturated fatty acids, or acombination thereof. In any aspect or embodiment described herein, thelow titer fatty acid material is or includes a distilled tall oil havingat least one of: an acid number of about 175 mg/g to about 200 mg/g,about 37.0 to about 43.0% rosin acid (e.g., about 40% rosin acid), aGardner Color Index equal to or less than 9 (e.g., about 7 to about 9),or a combination thereof. In any aspect or embodiment described herein,the low titer fatty acid material is or includes a distilled tall oilhaving at least one of: an acid number of about 182.0 mg/g to about 200mg/g (e.g., about 189 mg/g), about 25.0 to about 28.0% rosin acid (e.g.,about 26% rosin acids), a Gardner Color Index of equal to or less than 7(e.g., about 5 to about 7 or about 6), about 1.0% or less palmitic acid,about 6.0% or less pimaric acid, or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acidmaterial is or includes a mixture or blend of tall oil fatty acid anddistilled tall oil, wherein the low titer fatty acid material has arosin acid content as described herein. For example, in any aspect orembodiment described herein, the blend or mixture of tall oil fatty acidand distilled tall oil fatty acid is or includes Altapyne™ M-15 (about10% to about 15% or about 13% rosin acid content) (Ingevity Corp.,Charleston, S.C.). Thus, in any aspect or embodiment described herein,the low titer fatty acid material includes or is a distilled tall oilhaving at least one of: about 10 to about 15% rosin acid, an acid numberof about 175 mg/g to about 195 mg/g, a Gardner Color Index equal to orless than 10, a titer point of about 9 to about 11° C. (such as about10° C.), or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acidmaterial is or includes a mixture or blend of distilled tall oil androsin, wherein the low titer fatty acid material has a rosin acidcontent as described herein. For example, in any aspect or embodimentdescribed herein, the blend or mixture of distilled tall oil and rosinis or includes Altapyne™ M-32 (about 30% to about 34% or about 30% rosinacid) (Ingevity Corp., Charleston, S.C.). Thus, in any aspect orembodiment described herein, the low titer fatty acid material includesor is a distilled tall oil having at least one of: about 30% to about34% rosin acid, an acid number of about 170 mg/g to about 185 mg/g, aGardner Color Index of less than or equal to 12, a titer point of about10 to about 12° C. (such as about 11° C.), or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acidmaterial is or includes a mixture or blend of TOFA and rosin, whereinthe rosin acid content is as described herein. For example, in anyaspect or embodiment described herein, the blend or mixture of TOFA androsin is or includes Altapyne™ M-30D (e.g., about 26% to about 31% rosinacid) (Ingevity Corp., Charleston, S.C.). Thus, in any aspect orembodiment described herein, the low titer fatty acid material includesor is a blend or mixture of TOFA and rosin, wherein the low titer fattyacid material includes or is a blend or mixture of TOFA and rosin thathas at least one of: about 26% to about 31% rosin acid, an acid numberof about 180 mg/g to about 185 mg/g, about 64% to about 70% fatty acids,a Gardner Color Index equal to or less than 11, a titer point of about8° C. to about 12° C., or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acidmaterial is or includes a disproportionated tall oil, a mixture ofdisproportionated tall oil and rosin, a mixture of disproportionatedtall oil and TOFA, a mixture of disproportionated tall oil and distilledtall oil (DTO), or a combination thereof, wherein the low titer acidmaterial has a rosin acid content as described herein. For example, inany aspect or embodiment described herein, the low titer fatty acidmaterial is or includes Altapyne™ 1430 (Ingevity Corp., Charleston,S.C.). Thus, in any aspect or embodiment described herein, the low titerfatty acid material is or includes a disproportionated tall oil, havingat least one of: an acid number of about 170 to about 185 mg/g, about24% to about 30% rosin acid, a Gardner Color Index of no greater thanabout 12, about 60% to about 70% fatty acids, about 30% to about 40%oleic acid, about 8 to about 30% dehydroabietic acid, less than about1.0% abietic acid, or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acidmaterial is or includes at least one of SYLVATAL™ D25LR (e.g., a DTOcomposition with an acid number of about 186 mg/g, about 70% fattyacids, about 26% rosin acids, titer point of about 2° C.; ArizonaChemicals, Jascksonville, Fla.), SYLVATAL™ D30LR (e.g., a DTOcomposition with an acid number of about 185 mg/g, about 66% fattyacids, about 30% rosin acids, titer point of about 2 to about 10° C.(e.g., about 10° C.); Arizona Chemicals, Jascksonville, Fla.), SYLFATAL™D40LR (e.g., a DTO composition with an acid number of about 181 mg/g,about 58% fatty acids, about 39% rosin acids, titer point of about 2°C.; Arizona Chemicals, Jascksonville, Fla.), or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acidmaterial, low titer fatty acid material comprising rosin acid, or lowtiter rosin acid containing fatty acid material has an acid number ofabout 143 to about 200 mg/g. For example, in any aspect or embodimentdescribed herein, the low titer fatty acid material, low titer fattyacid material comprising rosin acid, or low titer rosin acid containingfatty acid material has an acid number of about 143 to about 200 mg/g,about 143 to about 195 mg/g, about 143 to about 190 mg/g, about 143 toabout 185 mg/g, about 143 to about 185 mg/g, about 143 to about 175mg/g, about 143 to about 170 mg/g, about 143 to about 165 mg/g, about143 to about 160 mg/g, about 143 to about 155 mg/g, about 143 to about150 mg/g, about 145 to about 200 mg/g, about 145 to about 195 mg/g,about 145 to about 190 mg/g, about 145 to about 185 mg/g, about 145 toabout 180 mg/g, about 145 to about 175 mg/g, about 145 to about 170mg/g, about 145 to about 165 mg/g, about 145 to about 160 mg/g, about145 to about 155 mg/g, about 145 to about 150 mg/g, about 150 to about200 mg/g, about 150 to about 195 mg/g, about 150 to about 190 mg/g,about 150 to about 185 mg/g, about 150 to about 180 mg/g, about 150 toabout 175 mg/g, about 150 to about 170 mg/g, about 150 to about 165mg/g, about 150 to about 160 mg/g, about 150 to about 155 mg/g, about155 to about 200 mg/g, about 155 to about 195 mg/g, about 155 to about190 mg/g, about 155 to about 185 mg/g, about 155 to about 180 mg/g,about 155 to about 175 mg/g, about 155 to about 170 mg/g, about 155 toabout 165 mg/g, about 155 to about 160 mg/g, about 160 to about 200mg/g, about 160 to about 195 mg/g, about 160 to about 190 mg/g, about160 to about 185 mg/g, about 160 to about 180 mg/g, about 160 to about175 mg/g, about 160 to about 170 mg/g, about 160 to about 165 mg/g,about 165 to about 200 mg/g, about 165 to about 195 mg/g, about 165 toabout 190 mg/g, about 165 to about 185 mg/g, about 165 to about 180mg/g, about 165 to about 175 mg/g, about 165 to about 170 mg/g, about170 to about 200 mg/g, about 170 to about 195 mg/g, about 170 to about190 mg/g, about 170 to about 185 mg/g, about 170 to about 180 mg/g,about 170 to about 175 mg/g, about 175 to about 185 mg/g, about 175 toabout 180 mg/g, about 180 to about 200 mg/g, about 180 to about 195mg/g, about 180 to about 190 mg/g, about 180 to about 185 mg/g, about185 to about 200 mg/g, about 185 to about 195 mg/g, about 185 to about190 mg/g, about 190 to about 200 mg/g, about 190 to about 195 mg/g, orabout 195 to about 500 mg/g. In any aspect or embodiment describedherein, the fatty acid material has an acid number of about 143, about144, about 145, about 146, about 147, about 148, about 149, about 150,about 151, about 152, about 153, about 154, about 155, about 156, about157, about 158, about 159, about 160, about 161, about 162, about 163,about 164, about 165, about 166, about 167, about 168, about 169, about170, about 171, about 172, about 173, about 174, about 175, about 176,about 177, about 178, about 179, about 180, about 181, about 182, about183, about 184, about 185, about 186, about 187, about 188, about 189,about 190, about 191, about 192, about 193, about 194, about 195, about196, about 197, about 198, about 199, or about 200 mg/g.

In any aspect or embodiment described herein, acid number can bedetermined by titration. For example, in any aspect or embodimentdescribed herein, acid number can be determined by titration with 0.5NKOH. An exemplary method to determine acid number through titration isdescribed below in the Examples.

In any aspect or embodiment described herein, the low titer fatty acidmaterial, low titer fatty acid material comprising rosin acid, or lowtiter rosin acid containing fatty acid material has a rosin acid (RA)concentration or content of about 11% to about 50% (e.g., about 11% toabout 41% or about 19% to about 28%). For example, in any aspect orembodiment described herein, the RA concentration of the low titer fattyacid material is about 11% to about 50%, about 11% to about 45%, about11% to about 41%, about 11% to about 35%, about 11% to about 30%, about11% to about 25%, about 11% to about 20%, about 15% to about 50%, about15% to about 45%, about 15% to about 41%, about 15% to about 35%, about15% to about 30%, about 15% to about 25%, about 20% to about 50%, about20% to about 45%, about 20% to about 41%, about 20% to about 35%, about20% to about 30%, about 25% to about 50%, about 25% to about 45%, about25% to about 41%, about 25% to about 35%, about 30% to about 50%, about30% to about 45%, about 30% to about 41%, about 35% to about 50%, about35% to about 45%, or about 40% to about 50%. The RA concentration can bedetermined by titration. For example, in certain embodiments, a modifiedGlidden procedure is utilized for RA concentration of about 15% or less,and for RA concentration of about 15% or greater a modified Wolfe Methodis utilized. Alternatively, the RA concentration can be determined bythe organic gel permeation chromatography. In any aspect or embodimentdescribed herein, the rosin acid includes or is at least one ofpalustric acid, abietic acid, neoabietic acid, pimaric acid, levopimaricacid, isopimaric acid, a disproportionated rosin acid (e.g.,dehydroabietic acid), or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acidmaterial, low titer fatty acid material comprising rosin acid, or lowtiter rosin acid containing fatty acid material, is or includes a streamfrom the tall oil fatty acid distillation or processing (e.g., crudetall oil refining). In an embodiment, the low titer fatty acid materialstream, low titer fatty acid material comprising rosin acid stream, orlow titer rosin acid containing fatty acid material stream is orincludes a by-product of crude tall oil refining process during theproduction of the light colored (Gardner color<7) highly pure TOFA(e.g., TOFA with a RA concentration of less than about 5% as determinedby titration).

In any aspect or embodiment described herein, the low titer fatty acidmaterial, low titer fatty acid material comprising rosin acid, or lowtiter rosin acid containing fatty acid material has a titer point<about14° C. (e.g., <about 13° C., <about 12° C., <about 11° C., <about 10°C., <about 9° C., <about 8° C., <about 7° C., <about 6° C., <about 5°C., <about 4° C., <about 3° C., <about 2° C., or <about 1° C.). In anyaspect or embodiment described herein, the fatty acid (FA) concentrationcan be in the range of about 34% to about 89% (e.g., about 34% to about76% or about 40%-about 60%). For example, in any aspect or embodimentdescribed herein, the fatty acid concentration in the low titer fattyacid material, low titer fatty acid material comprising rosin acid, orlow titer rosin acid containing fatty acid material is about 34% toabout 89%, about 34% to about 80%, about 34% to about 70%, about 34% toabout 60%, about 34% to about 50%, about 34% to about 40%, about 40% toabout 89%, about 40% to about 80%, about 40% to about 70%, about 40% toabout 60%, about 40% to about 50%, about 50% to about 89%, about 50% toabout 80%, about 50% to about 70%, about 50% to about 60%, about 60% toabout 89%, about 60% to about 80%, about 60% to about 70%, about 70% toabout 89%, about 70% to about 80%, or about 80% to about 89%. In anyaspect or embodiment described herein, the low titer fatty acidmaterial, low titer fatty acid material comprising rosin acid, or lowtiter rosin acid containing fatty acid material includes at least oneof: C18 type fatty acids is present in an amount of about 25 to about89% (e.g., about 25 to about 77%); C20 type fatty acids is present in anamount of less than or equal to about 34% (e.g., about 0.4 to about 34%or about 8 to about 34%), C16 type fatty acids is present in an amountof no greater than about 5% (e.g., no greater than about 4%, no greaterthan about 3%, no greater than about 2%; no greater than about 1%, or acombination thereof. For example, in any aspect or embodiment describedherein, the low titer fatty acid material includes C18 fatty acidspresent in an amount of about 25 to about 89%, about 25 to about 80%,about 25 to about 70%, about 25 to about 60%, about 25 to about 50%,about 25 to about 40%, about 25 to about 35%, about 35 to about 89%,about 35 to about 80%, about 35 to about 70%, about 35 to about 60%,about 35 to about 50%, about 35 to about 45%, about 45 to about 89%,about 45 to about 80%, about 45 to about 70%, about 45 to about 60%,about 45 to about 55%, about 55 to about 89%, about 55 to about 80%,about 55 to about 70%, about 55 to about 65%, about 65 to about 89%,about 65 to about 80%, about 65 to about 75%, about 65 to about 89%,about 65 to about 80%, about 65 to about 75%, about 75 to about 89%,about 75 to about 85%, or about 80 to about 89%. In any aspect orembodiment described herein, the low titer fatty acid material includesC20 fatty acids present in an amount of ≤about 34%, ≤about 30%, ≤about25%, ≤about 20%, ≤about 15%, ≤about 10%, ≤about 5%, about 0.4 to about34%, about 0.4 to about 30%, about 0.4 to about 25%, about 0.4 to about20%, about 0.4 to about 15%, about 0.4 to about 10%, about 0.4 to about5%, about 5 to about 34%, about 5 to about 30%, about 5 to about 25%,about 5 to about 20%, about 5 to about 15%, about 5 to about 10%, about10 to about 34%, about 10 to about 30%, about 10 to about 25%, about 10to about 20%, about 10 to about 15%, about 15 to about 34%, about 15 toabout 30%, about 15 to about 25%, about 15 to about 20%, about 20 toabout 34%, about 20 to about 30%, about 20 to about 25%, about 25 toabout 34%, about 25 to about 30%, or about 30 to about 35%. In anyaspect or embodiment described herein, the titer point can be determinedvia ASTM D1982-61 or the exemplary method described in the Examples.

The fatty acid concentration and/or content can be determined by organicgel permeation chromatography (GPC), e.g., GPC using tetrahydrofuran(THF) as the mobile phase and refractive index detector. Since GPC alonecannot differentiate and estimate different carbon chain lengths in thefatty acid. Further determination of the fatty acid type and percentageis estimated by the combination of GPC and gas chromatography (GC)methods, wherein the correction factor for the heavies is determined bythe GPC method. Thus, for example, from the GC method of analysis thefatty acid content, the low titer fatty acid material, low titer fattyacid material comprising rosin acid, or low titer rosin acid containingfatty acid material can include: predominantly C18 type fatty acid(e.g., about 25-about 89% or about 25-about 77%), less than or equal toabout 34% (e.g., about 0.4 to about 34% or about 8 to about 34%) C20type fatty acids; minor components of C16 type fatty acids (e.g., ≤about5%, ≤about 4%, ≤about 3%, ≤about 2%, or about 0.5 to about 3%); or acombination thereof.

In any aspect or embodiment described herein, the fatty acid material orlow titer fatty acid material, low titer fatty acid material comprisingrosin acid, or low titer rosin acid containing fatty acid materialcomprises a PAN rosin acid (e.g., palustric, abietic, and/or theneoabietic acid) concentration or content of less than or equal to about50% (e.g., about 0.25% to about 50%, less than or equal to about 11%, orabout 0.25% to about 11%). For example, in any aspect or embodimentdescribed herein, the PAN rosin acid concentration or content of the lowtiter fatty acid material, low titer fatty acid material comprisingrosin acid, or low titer rosin acid containing fatty acid material isequal to or less than about 50%, equal to or less than about 45%, equalto or less than about 40%, equal to or less than about 35%, equal to orless than about 30%, equal to or less than about 25%, equal to or lessthan about 20%, equal to or less than about 15%, equal to or less thanabout 11%, less than or equal to about 10%, less than or equal to about9%, less than or equal to about 8%, less than or equal to about 7%, lessthan or equal to about 6%, less than or equal to about 5%, less than orequal to about 4%, less than or equal to about 3%, about 0.25% to about50%, about 0.25% to about 45%, about 0.25% to about 35%, about 0.25% toabout 30%, about 0.25% to about 25%, about 0.25% to about 20%, about0.25% to about 15%, about 0.25% to about 10%, about 0.25% to about 5%,about 5% to about 50%, about 5% to about 45%, about 5% to about 35%,about 5% to about 30%, about 5% to about 25%, about 5% to about 20%,about 5% to about 15%, about 5% to about 10%, about 10% to about 50%,about 10% to about 45%, about 10% to about 35%, about 10% to about 30%,about 10% to about 25%, about 10% to about 20%, about 10% to about 15%,about 15% to about 50%, about 15% to about 45%, about 15% to about 35%,about 15% to about 30%, about 15% to about 25%, about 15% to about 20%,about 20% to about 50%, about 20% to about 45%, about 20% to about 35%,about 20% to about 30%, about 20% to about 25%, about 25% to about 50%,about 25% to about 45%, about 25% to about 35%, about 25% to about 30%,about 30% to about 50%, about 30% to about 45%, about 30% to about 35%,about 35% to about 50%, about 35% to about 45%, about 35% to about 40%,about 40% to about 50%, about 40% to about 45%, about 45% to about 40%,about 0.25% to about 11%, about 0.25% to about 10%, about 0.25% to about9%, about 0.25% to about 8%, about 0.25% to about 7%, about 0.25% toabout 6%, about 0.25% to about 5%, about 0.25% to about 4%, about 0.25%to about 3%, about 1% to about 11%, about 1% to about 10%, about 1% toabout 9%, about 1% to about 8%, about 1% to about 7%, about 1% to about6%, about 1% to about 5%, about 1% to about 4%, about 1% to about 3%,about 2% to about 11%, about 2% to about 10%, about 2% to about 9%,about 2% to about 8%, about 2% to about 7%, about 2% to about 6%, about2% to about 5%, about 2% to about 4%, about 3% to about 11%, about 3% toabout 10%, about 3% to about 9%, about 3% to about 8%, about 3% to about7%, about 3% to about 6%, about 3% to about 5%, about 4% to about 11%,about 4% to about 10%, about 4% to about 9%, about 4% to about 8%, about4% to about 7%, about 4% to about 6%, about 5% to about 11%, about 5% toabout 10%, about 5% to about 9%, about 5% to about 8%, about 5% to about7%, about 6% to about 11%, about 6% to about 10%, about 6% to about 9%,about 6% to about 8%, about 7% to about 11%, about 7% to about 10%,about 7% to about 9%, about 8% to about 11%, about 8% to about 10%, orabout 9% to about 11%. For example, in particular embodiments, the lowtiter fatty acid material, low titer fatty acid material comprisingrosin acid, or low titer rosin acid containing fatty acid material has aPAN rosin acid concentration or content of about 0.5%, about 1%, about1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%,about 5%, about 5.5%, about 6%, about 6.5%, about 7%, about 7.5%, about8%, about 8.5%, about 9%, about 9.5%, about 10%, about 10.5%, about 11%,about 11.5%, about 12%, about 12.5%, about 13%, about 13.5%, about 14%,about 14.5%, about 15%, about 15.5%, about 16%, about 16.5%, about 17%,about 17.5%, about 18%, about 18.5%, about 19%, about 19.5%, about 20%,about 20.5%, about 21%, about 21.5%, about 22%, about 22.5%, about 23%,about 23.5%, about 24%, about 24.5%, about 25%, about 25.5%, about 26%,about 26.5%, about 27%, about 27.5%, about 28%, about 28.5%, about 29%,about 29.5%, about 30%, about 30.5%, about 31%, about 31.5%, about 32%,about 32.5%, about 33%, about 33.5%, about 34%, about 34.5%, about 35%,about 35.5%, about 36%, about 36.5%, about 37%, about 37.5%, about 38%,about 38.5%, about 39%, about 39.5%, about 40%, about 40.5%, about 41%,about 41.5%, about 42%, about 42.5%, about 43%, about 43.5%, about 44%,about 44.5%, about 45%, about 45.5%, about 46%, about 46.5%, about 47%,about 47.5%, about 48%, about 48.5%, about 49%, about 49.5%, or about50%.

PAN rosin acid concentration/content can be determined by GC. Forexample, in any aspect or embodiment described herein, the PAN rosinacid concentration/content can be determined according to ASTM D-5974-15or a modification thereof, which are within the general knowledge ofthose skilled in the art. For example, the ASTM D-5974-15 method can bemodified by using, e.g., a non-polar column (e.g., SPB-5), instead of apolar column, to allow for the use of high temperatures, which allowsfor substances with higher boiling points to elute out from the column,and/or faster heating rates, which can accelerate the analysis. In anyaspect or embodiment described herein, the correction factor for heaviesestimation can be determined by the GPC method. PAN rosin acidconcentration/content can alternatively be determined by GS-MassSpectroscopy utilizing the ASTM D-5974-15 method, includingmodifications that one skilled in the art would appreciate (such as, anon-polar column may be utilized to allow for faster heating rates andhigher temperature, which accelerates the analysis).

In any aspect or embodiment described herein, the heavies in the lowtiter fatty acid material (i.e., the low titer fatty acid materialcomprising rosin acid) is less than or equal to about 40% (e.g., about0.5 to about 40%, about 5 to about 40%, about 5 to about 35%, or about15 to about 28%) of the low titer fatty acid composition. In any aspector embodiment described herein, the heavies are dimer and trimer fattyor rosin acids that have a higher boiling point than the monomer fattyand rosin acids, which are usually formed during the distillationprocess. In any aspect or embodiment described herein, the concentrationand content of heavies in the low titer fatty acid material can bedetermined, e.g., by the GPC. For example, in certain embodiments, thelow titer fatty acid material (i.e., the low titer rosin acid containingfatty acid material) comprises ≤about 40%, ≤about 35%, ≤about 30%,≤about 25%, ≤about 20%, ≤about 15%, ≤about 10%, ≤about 5%, about 0.5% toabout 40%, about 0.5% to about 35%, about 0.5% to about 30%, about 0.5%to about 25%, about 0.5% to about 20%, about 0.5% to about 15%, about0.5% to about 10%, about 0.5% to about 5%, about 5% to about 40%, about5% to about 35%, about 5% to about 30%, about 5% to about 25%, about 5%to about 20%, about 5% to about 15%, about 5% to about 10%, about 10% toabout 40%, about 10% to about 35%, about 10% to about 30%, about 10% toabout 25%, about 10% to about 20%, about 10% to about 15%, about 15% toabout 40%, about 15% to about 35%, about 15% to about 30%, about 15% toabout 25%, about 15% to about 20%, about 20% to about 50%, about 20% toabout 35%, about 20% to about 30%, about 20% to about 25%, about 25% toabout 40%, about 25% to about 35%, about 25% to about 30%, about 30% toabout 40%, or about 35% to about 40% heavies from the tall oildistillation process or crude tall oil refining (e.g., dimers, trimmers,or other heavier components).

In any aspect or embodiment described herein, the low titer fatty acidmaterial, low titer fatty acid material comprising rosin acid, or lowtiter rosin acid containing fatty acid material has a Gardner colorindex in a range from about 4.0 to about 17.0 (e.g., about 4.0 to about14.7, about 6.0 to about 14.7, or about 9.0 to about 13.0). For example,in certain embodiments, the low titer fatty acid material has a Gardnercolor index of about 4.0 to about 17.0, about 4.0 to about 15.0, about4.0 to about 14.7, about 4.0 to about 13.0, about 4.0 to about 12.0,about 4.0 to about 10.0, about 4.0 to about 8.0, about 4.0 to about 6.0,about 6.0 to about 17.0, about 6.0 to about 15.0, about 6.0 to about14.7, about 6.0 to about 13.0, about 6.0 to about 12.0, about 6.0 toabout 10.0, about 6.0 to about 8.0, about 8.0 to about 17.0, about 8.0to about 15.0, about 8.0 to about 14.7, about 8.0 to about 13.0, about8.0 to about 12.0, about 8.0 to about 10.0, about 10.0 to about 17.0,about 10.0 to about 15.0, about 10.0 to about 14.7, about 10.0 to about13.0, about 10.0 to about 12.0, about 12.0 to about 17.0, about 12.0 toabout 15.0, about 12.0 to about 14.0, or about 14.0 to about 17.0. Inany aspect or embodiment described herein, the Gardner color index isdetermined with ASTM D6166-12 (2016).

In any aspect or embodiment described herein, the low titer fatty acidmaterial, low titer fatty acid material comprising rosin acid, or lowtiter rosin acid containing fatty acid material has a Chemical AbstractsService Registry (CAS) No. 8002-26-4; a blend or mixture of a tall oilwith a CAS No. 8002-26-4 and a TOFA with a CAS No. 61790-12-3; a blendor mixture of CAS No. 8050-09-7 (Resin-95 or rosin R-24) and a TOFA witha CAS No. 61790-12-3; a blend or mixture of CAS No. 8002-26-4, CAS No.61790-12-3, and CAS No. 8050-09-7; or a dis-proportionated tall oil witha CAS No. 68152-92-1 optionally blended or mixed with another low titerfatty acid material, TOFA, DTO, or tall oil.

Amine Material

In any aspect or embodiment described herein, the amine materialincludes at least one of diethylenetriamine (DETA),hydroxyethyldiethylenetriamine (HEDETA), 2-piperazinoethanol,triethylenetetramine (TETA), Tetraethylenepentamine mixtures (TEPA),pentaethylene hexamine (PEHA) heptaethyleneoctamine (HEOA),hexaethyleneheptamine (HEHA)amine HST, amine DCT, aminoethylpiperazine(AEP), dimethylaminopropylamine (DMAPA), aminoethylethanolamine (AEEA),diethanolamine (DEA), triethanolamine (TEA), monoethanolamine, otherhigher ethylene amines or a combination thereof.

In any aspect or embodiment described herein the amine material has anamine value of about 700 to about 1300 mg/g (e.g., about 700 mg/g toabout 900 mg/g). For example, in any aspect or embodiment describedherein, the amine material has an amine value of about 700 to about 1300mg/g, about 700 to about 1200 mg/g, about 700 to about 1100 mg/g, about700 to about 1000 mg/g, about 700 to about 900 mg/g, about 700 to about875 mg/g, about 700 to about 850 mg/g, about 700 to about 825 mg/g,about 700 to about 800 mg/g, about 700 to about 775 mg/g, about 700 toabout 750 mg/g, about 700 to about 725 mg/g, about 725 to about 1300mg/g, about 725 to about 1200 mg/g, about 725 to about 1100 mg/g, about725 to about 1000 mg/g, about 725 to about 900 mg/g, about 725 to about875 mg/g, about 725 to about 850 mg/g, about 725 to about 825 mg/g,about 725 to about 800 mg/g, about 725 to about 775 mg/g, about 725 toabout 750 mg/g, about 750 to about 1300 mg/g, about 750 to about 1200mg/g, about 750 to about 1100 mg/g, about 750 to about 1000 mg/g, about750 to about 900 mg/g, about 750 to about 875 mg/g, about 750 to about850 mg/g, about 750 to about 825 mg/g, about 750 to about 800 mg/g,about 750 to about 775 mg/g, about 775 to about 1300 mg/g, about 775 toabout 1200 mg/g, about 775 to about 1100 mg/g, about 775 to about 1000mg/g, about 775 to about 900 mg/g, about 775 to about 875 mg/g, about775 to about 850 mg/g, about 775 to about 825 mg/g, about 775 to about800 mg/g, about 800 to about 1300 mg/g, about 800 to about 1200 mg/g,about 800 to about 1100 mg/g, about 800 to about 1000 mg/g, about 800 toabout 900 mg/g, about 800 to about 875 mg/g, about 800 to about 850mg/g, about 800 to about 825 mg/g, about 835 to about 1300 mg/g, about825 to about 1200 mg/g, about 825 to about 1100 mg/g, about 825 to about1000 mg/g, about 825 to about 900 mg/g, about 825 to about 875 mg/g,about 825 to about 850 mg/g, about 850 to about 1300 mg/g, about 850 toabout 1200 mg/g, about 850 to about 1100 mg/g, about 850 to about 1000mg/g, about 850 to about 900 mg/g, about 850 to about 875 mg/g, about875 to about 1300 mg/g, about 875 to about 1200 mg/g, about 875 to about1100 mg/g, about 875 to about 1000 mg/g, about 875 to about 900 mg/g,about 900 to about 1300 mg/g, about 900 to about 1200 mg/g, about 900 toabout 1100 mg/g, about 900 to about 1000 mg/g, about 1000 to about 1300mg/g, about 1000 to about 1200 mg/g, about 1000 to about 1100 mg/g,about 1100 to about 1300 mg/g, about 1100 to about 1200 mg/g, about 1100to about 1300 mg/g, about 1100 to about 1200 mg/g, or about 1200 toabout 1300 mg/g. In any aspect or embodiment described herein, the aminematerial has an amine value of about 700, about 701, about 702, about703, about 704, about 705, about 706, about 707, about 708, about 709,about 710, about 711, about 712, about 713, about 714, about 715, about716, about 717, about 718, about 719, about 720, about 721, about 722,about 723, about 724, about 725, about 726, about 727, about 728, about729, about 730, about 731, about 732, about 733, about 734, about 735,about 736, about 737, about 738, about 739, about 740, about 741, about742, about 743, about 744, about 745, about 746, about 747, about 748,about 749, about 750, about 751, about 752, about 753, about 754, about755, about 756, about 757, about 758, about 759, about 760, about 761,about 762, about 763, about 764, about 765, about 767, about 768, about769, or about 770, about 771, about 772, about 773, about 774, about775, about 776, about 777, about 778, about 779, about 780, about 781,about 782, about 783, about 784, about 785, about 786, about 787, about788, about 789, about 790, about 791, about 792, about 793, about 794,about 795, about 796, about 797, about 798, about 799, about 800, about801, about 802, about 803, about 804, about 805, about 806, about 807,about 808, about 809, about 810, about 811, about 812, about 813, about814, about 815, about 816, about 817, about 818, about 819, about 820,about 821, about 822, about 823, about 824, about 825, about 826, about827, about 828, about 829, about 830, about 831, about 832, about 833,about 834, about 835, about 836, about 837, about 838, about 839, about840, about 841, about 842, about 843, about 844, about 845, about 846,about 847, about 848, about 849, about 850, about 851, about 852, about853, about 854, about 855, about 856, about 857, about 858, about 859,about 860, about 861, about 862, about 863, about 864, about 865, about867, about 868, about 869, about 870, about 871, about 872, about 873,about 874, about 875, about 876, about 877, about 878, about 879, about880, about 881, about 882, about 883, about 884, about 885, about 886,about 887, about 888, about 889, about 890, about 891, about 892, about893, about 894, about 895, about 896, about 897, about 898, about 899,about 900 mg/g, about 901, about 902, about 903, about 904, about 905,about 906, about 907, about 908, about 909, about 910, about 911, about912, about 913, about 914, about 915, about 916, about 917, about 918,about 919, about 920, about 921, about 922, about 923, about 924, about925, about 926, about 927, about 928, about 929, about 930, about 931,about 932, about 933, about 934, about 935, about 936, about 937, about938, about 939, about 940, about 941, about 942, about 943, about 944,about 945, about 946, about 947, about 948, about 949, about 950, about951, about 952, about 953, about 954, about 955, about 956, about 957,about 958, about 959, about 960, about 961, about 962, about 963, about964, about 965, about 967, about 968, about 969, about 970, about 971,about 972, about 973, about 974, about 975, about 976, about 977, about978, about 979, about 980, about 981, about 982, about 983, about 984,about 985, about 986, about 987, about 988, about 989, about 990, about991, about 992, about 993, about 994, about 995, about 996, about 997,about 998, about 999, about 1000, about 1001, about 1002, about 1003,about 1004, about 1005, about 1006, about 1007, about 1008, about 1009,about 1010, about 1011, about 1012, about 1013, about 1014, about 1015,about 1016, about 1017, about 1018, about 1019, about 1020, about 1021,about 1022, about 1023, about 1024, about 1025, about 1026, about 1027,about 1028, about 1029, about 1030, about 1031, about 1032, about 1033,about 1034, about 1035, about 1036, about 1037, about 1038, about 1039,about 1040, about 1041, about 1042, about 1043, about 1044, about 1045,about 1046, about 1047, about 1048, about 1049, about 1050, about 1051,about 1052, about 1053, about 1054, about 1055, about 1056, about 1057,about 1058, about 1059, about 1060, about 1061, about 1062, about 1063,about 1064, about 1065, about 1067, about 1068, about 1069, about 1070,about 1071, about 1072, about 1073, about 1074, about 1075, about 1076,about 1077, about 1078, about 1079, about 1080, about 1081, about 1082,about 1083, about 1084, about 1085, about 1086, about 1087, about 1088,about 1089, about 1090, about 1091, about 1092, about 1093, about 1094,about 1095, about 1096, about 1097, about 1098, about 1099, about 1100,about 1101, about 1102, about 1103, about 1104, about 1105, about 1106,about 1107, about 1108, about 1109, about 1110, about 1111, about 1112,about 1113, about 1114, about 1115, about 1116, about 1117, about 1118,about 1119, about 1121, about 1121, about 1122, about 1123, about 1124,about 1125, about 1126, about 1127, about 1128, about 1129, about 1131,about 1131, about 1132, about 1133, about 1134, about 1135, about 1136,about 1137, about 1138, about 1139, about 1141, about 1141, about 1142,about 1143, about 1144, about 1145, about 1146, about 1147, about 1148,about 1149, about 1151, about 1151, about 1152, about 1153, about 1154,about 1155, about 1156, about 1157, about 1158, about 1159, about 1161,about 1161, about 1162, about 1163, about 1164, about 1165, about 1167,about 1168, about 1169, about 1171, about 1171, about 1172, about 1173,about 1174, about 1175, about 1176, about 1177, about 1178, about 1179,about 1181, about 1181, about 1182, about 1183, about 1184, about 1185,about 1186, about 1187, about 1188, about 1189, about 1191, about 1191,about 1192, about 1193, about 1194, about 1195, about 1196, about 1197,about 1198, about 1199, about 1200, about 1201, about 1202, about 1203,about 1204, about 1205, about 1206, about 1207, about 1208, about 1209,about 1210, about 1211, about 1212, about 1213, about 1214, about 1215,about 1216, about 1217, about 1218, about 1219, about 1221, about 1221,about 1222, about 1223, about 1224, about 1225, about 1226, about 1227,about 1228, about 1229, about 1231, about 1231, about 1232, about 1233,about 1234, about 1235, about 1236, about 1237, about 1238, about 1239,about 1241, about 1241, about 1242, about 1243, about 1244, about 1245,about 1246, about 1247, about 1248, about 1249, about 1251, about 1251,about 1252, about 1253, about 1254, about 1255, about 1256, about 1257,about 1258, about 1259, about 1261, about 1261, about 1262, about 1263,about 1264, about 1265, about 1267, about 1268, about 1269, about 1271,about 1271, about 1272, about 1273, about 1274, about 1275, about 1276,about 1277, about 1278, about 1279, about 1281, about 1281, about 1282,about 1283, about 1284, about 1285, about 1286, about 1287, about 1288,about 1289, about 1291, about 1291, about 1292, about 1293, about 1294,about 1295, about 1296, about 1297, about 1298, about 1299, or about1300 mg/g.

In any aspect or embodiment described herein, amine value can bedetermined through titration. For example, in any aspect or embodimentdescribed herein, amine value can be determined by titration with 0.5NHCl. An exemplary method that may be used to determine amine valuethrough titration is described below in the Examples.

In any aspect or embodiments described herein, the amine material is orincludes the chemical composition having Chemical Abstracts Service(CAS) Registry No. 68910-05-4. This composition is the distillationresiduum bottoms composition remaining from the process whereinmonoethanolamine (i.e., 2-aminoethanol) is reacted with ammonia toproduce a reaction product which is then fractionated to recover apiperazine distillate product therefrom, thus leaving the remaining CASReg. No. 68910-05-4 distillation residuum bottoms composition. Thedistillation residuum bottoms composition CAS Reg. No. 68910-05-4 iscommercially available, for example, from Dow® Chemical Co.(Marlborough, Mass.) under the name AMINE HST and is also available fromBASF under the name AMIX 1000 or Berolamine 20 (BA-20). AMINE HST has:an estimated boiling point (760 mmHg) of 256° C., an estimatedflashpoint (closed cup) of 146° C., an estimated vapor pressure of lessthan 0.01 mmHg at 20° C., an estimated vapor density (air=1) of 4.6, anestimated specific gravity (water=1) of 1.0-1.3 at 20° C./20° C., anestimated solubility in water of 100% by weight at 20° C., and anestimated pour point of −24° C.

Thus, in any aspect or embodiment described herein, the amine materialis or includes a chemical composition having CAS Registry No.68910-05-4, such as at least one of: AMINE HST (e.g., an amine materialhaving at least one of: an estimated boiling point (760 mmHg) of 256°C., an estimated flashpoint (closed cup) of 146° C., an estimated vaporpressure of less than 0.01 mmHg at 20° C., an estimated vapor density(air=1) of 4.6, an estimated specific gravity (water=1) of 1.0-1.3 at20° C./20° C., an estimated solubility in water of 100% by weight at 20°C., an estimated pour point of −24° C., or a combination thereof), BA-20(e.g., an amine material having at least one of: an amine value of atleast 1100 mg/g, a viscosity at 50° C. that is equal to or less than100, a melting or freezing point of at 1013 hPa that is less than −30°C., a boiling point at 1013 hPa of about 254° C., a flash point at 1013hPa of about 176° C., a viscosity (such as a dynamic viscosity) at 50°C. of about 40 mPa·s, an auto-ignition temperature at 1013 hPa of about355° C., a relative density at 20° C. of about 1024, about 45%alkanolamines (e.g., AEEA, DEA, hydroxymethyl DETA, and higher orderalkanolamines), a vapor pressure at 20° C. of about 0.00009 hPa, about55% higher polyethylene polyamines (e.g., isomers of TETA, TEPA, PEHA,and higher order polyethylene polyamines), or AMIX 1000 (e.g., an aminematerial having at least one of: an amine value of about 1000 mg/g, amelting temperature of about −30° C., a boiling temperature of about236° C. to about 310° C., a density at 20° C. of about 1.04 g/cm³, aflash point of about 132° C., an ignition temperature of about 360° C.,or a combination thereof).

Method of Making the LGS Tolerant Emulsifier

The present disclosure also provides methods of making a LGS tolerantemulsifier (i.e, a MDTA emulsifier or a LGS tolerant MDTA emulsifier),the method comprising: reacting the low titer fatty acid material anamine material to produce an amido-amine reaction product; and reactingthe amido-amine reaction product with maleic anhydride to produce amaleated amido-amine reaction product.

In any aspect or embodiment described herein, the method of making a LGStolerant MDTA emulsifier comprising reacting a low titer fatty acidmaterial and an amine material at room temperature and then elevatedtemperatures to produce an amido-amine reaction product; and reactingthe amido-amine reaction product with maleic anhydride at elevatedtemperature to produce a maleated-amido-amine reaction product. In anyaspect or embodiment described herein, the method of making a LGStolerant MDTA emulsifier comprising reacting a low titer fatty acidmaterial and an amine material at room temperature first, followed byheating to about 110 to about 150° C. (e.g., from about 130 to about140° C.), followed by heating to about 175 to about 250° C. (e.g., fromabout 200 to about 225° C.), to produce an amido-amine reaction product;and reacting the amido-amine reaction product with maleic anhydride atabout 60 to about 90°, and optionally hold for up to about 1 hour (e.g.,about 30 minutes), to produce a maleated amido-amine reaction product.In certain embodiments, the fatty acid material and amine material areincubated at the elevated temperature for up to about 4 hours (e.g.,about 3 hours, about 2 hours, about 1 hour, about 1 to about 4 hours,about 1 to about 3 hours, about 1 to about 2 hours, about 2 to about 4hours, about 2 to about 3 hours, or about 3 hours to about 4 hours).

Invert Emulsion Fluid

Another aspect of the present disclosure provides an invert emulsionfluid (IEF) comprising the emulsifier of the present disclosure and atleast one of: a non-aqueous continuous phase, a discontinuoushygroscopic phase like brine, an additive, or a combination thereof. Inany aspect or embodiment described herein, the additive includes atleast one of (e.g., 1, 2, 3, 4, 5, or 6, or more) a rheology modifier,emulsifier, wetting agents, viscosifiers, lime, salts, fluid lossadditives, lost circulation materials, weighting agents, or acombination thereof. The IEF of the present disclosure demonstrated thesurprising and unexpected ability to control (i.e., reduced) rheologyeven in the presence of relatively high concentrations of LGS ascompared to a maleated TOFA amine emulsifier, which is generallyrecognized as the industry standard, as disclosed in, e.g., U.S. Pat.No. 8,927,468 B2, which is incorporated herein by reference in itsentirety, including a non-spray dried version of the emulsifier (seee.g., page 4 of U.S. Pat. No. 8,927,468 B2).

In any aspect or embodiment described herein, the IEF comprises a highvolume, amount, or concentration of LGS. For example, the invertedemulsion fluid can comprise from about 4% to about 12% V/V of lowgravity solids. For example, in any aspect or embodiment describedherein, the IEF comprises about 4% to about 12%, about 4% to about 10%,about 4% to about 8%, about 4% to about 6%, about 6% to about 12%, about6% to about 10%, about 6% to about 8%, about 8% to about 12%, about 8%to about 10%, or about 10% to about 12% V/V of low gravity solids. Inany aspect or embodiment described herein, the IEF comprises about 4%,about 4.5%, about 5%, about 5.5%, about 6%, about 6.5%, about 7%, about7.5%, about 8%, about 8.5%, about 9%, about 9.5%, about 10%, about10.5%, about 11%, about 11.5%, or about 12% V/V of low gravity solids.

In any aspect or embodiment described herein, the LGS have a specificgravity of about 2.0 to about 3.0. For example, in certain embodiments,the LGS has a specific gravity of about 2.0 to about 3.0, about 2.0 toabout 2.9, about 2.0 to about 2.8, about 2.0 to about 2.7, about 2.0 toabout 2.6, about 2.0 to about 2.5, about 2.0 to about 2.4, about 2.0 toabout 2.3, about 2.0 to about 2.2, about 2.0 to about 2.1, about 2.1 toabout 3.0, about 2.1 to about 2.9, about 2.1 to about 2.8, about 2.1 toabout 2.7, about 2.1 to about 2.6, about 2.1 to about 2.5, about 2.1 toabout 2.4, about 2.1 to about 2.3, about 2.1 to about 2.2, about 2.2 toabout 3.0, about 2.2 to about 2.9, about 2.2 to about 2.8, about 2.2 toabout 2.7, about 2.2 to about 2.6, about 2.2 to about 2.5, about 2.2 toabout 2.4, about 2.2 to about 2.3, about 2.3 to about 3.0, about 2.3 toabout 2.9, about 2.3 to about 2.8, about 2.3 to about 2.7, about 2.3 toabout 2.6, about 2.3 to about 2.5, about 2.3 to about 2.4, about 2.4 toabout 3.0, about 2.4 to about 2.9, about 2.4 to about 2.8, about 2.4 toabout 2.7, about 2.4 to about 2.6, about 2.4 to about 2.5, about 2.5 toabout 3.0, about 2.5 to about 2.9, about 2.5 to about 2.8, about 2.5 toabout 2.7, about 2.5 to about 2.6, about 2.6 to about 3.0, about 2.6 toabout 2.9, about 2.6 to about 2.8, about 2.6 to about 2.7, about 2.7 toabout 3.0, about 2.7 to about 2.9, about 2.7 to about 2.8, about 2.8 toabout 3.0, about 2.8 to about 2.9, or about 2.9 to about 30. In certainembodiments, the LGS has a specific gravity of about 2.0, 2.1, 2.2, 2.3,2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0.

In any aspect or embodiment described herein, the low gravity solids areargillaceous solids. In any aspect or embodiment described herein, theLGS are drill solids. In any aspect or embodiment described herein, theLGS is or includes calcium montmorillonite. For example, the LGS can beREV DUST® (MILWHITE, INC., Brownsville, TV).

In any aspect or embodiment described herein, the IEF of the presentdisclosure has a low fluid loss, e.g. a fluid loss of no greater than(i.e., less than or equal to) about 20 mL at 350° F. in about 30minutes. Thus, the IEF of the present disclosure does not compromise onfluid loss performance and has sufficient emulsion stability for aworkable fluid.

In any aspect or embodiment described herein, the IEF of the presentdisclosure has a low HTHP fluid loss, e.g., a fluid loss between about 1and about 20 mL at 350° F. in about 30 minutes. See, e.g., APIRecommended Practice 13B-2, Fourth Edition, Recommended Practice forField Testing of Oil-based Drilling Fluids, for the test method toconduct the HTHP filtration test, i.e., at the test temperatureindicated. Thus, the IEF of the present disclosure do not compromise ontheir fluid loss performance and have sufficient emulsion stability fora workable fluid. For example, in any aspect or embodiment describedherein, the fluid loss of the IEF of the present disclosure is about 1mL to about 20 mL, about 1 mL to about 15 mL, about 1 mL to about 10 mL,about 1 mL to about 5 mL, about 5 mL to about 20 mL, about 5 mL to about15 mL, about 5 mL to about 10 mL, about 10 mL to about 20 mL, about 10mL to about 15 mL, or about 15 mL to about 20 mL.

In any aspect or embodiment described herein, the IEF of the presentdisclosure has a lower rheology than a similarly formulated IEFcomprising a maleated TOFA amine emulsifier. In an embodiment, the IEFof the present disclosure has a rheology that is lower than a similarlyformulated IEF comprising a maleated TOFA amine emulsifier as determinedby a decrease in Fann 35 rheometer readings from 600 rotations perminute (rpm) to 3 rpm, e.g., at 150° F. In certain embodiments, the IEFof the present disclosure has a rheology that is about 10-about 92%(e.g., about 10 to about 92% or about 50 to about 92%) lower than asimilarly formulated IEF comprising a maleated TOFA amine emulsifier asdetermined by Fann 35 rheometer readings from 600 rpm to 3 rpm at 150°F. For example, in any aspect or embodiment described herein, the IEF ofthe present disclosure has a rheology, as determined by Fann 35rheometer readings from 600 rpm to 3 rpm at 150° F., that is about 10 toabout 92%, about 10 to about 95%, about 10 to about 80%, about 10 toabout 70%, about 10 to about 60%, about 10 to about 50%, about 10 toabout 40%, about 10 to about 30%, about 20 to about 92%, about 20 toabout 85%, about 20 to about 80%, about 20 to about 70%, about 20 toabout 60%, about 20 to about 50%, about 20 to about 40%, about 30 toabout 92%, about 30 to about 85%, about 30 to about 80%, about 30 toabout 70%, about 30 to about 60%, about 30 to about 50%, about 40 toabout 92%, about 40 to about 85%, about 40 to about 80%, about 40 toabout 70%, about 40 to about 60%, about 50 to about 92%, about 50 toabout 85%, about 50 to about 80%, about 50 to about 70%, about 60 toabout 92%, 60 to about 85%, about 60 to about 80%, or about 70 to about92% lower than a similarly formulated IEF comprising a maleated TOFAamine emulsifier. In any of the aspects or embodiments described herein,the rheology of the IEF is determined at 100 ppb REVDUST tested understandard conditions. In any aspect or embodiment described herein, HPHTfluid loss and rheology are determined using the methods/conditionsdescribed in API Recommended Practice 13B-2, Fourth Edition, RecommendedPractice for Field Testing of Oil-based Drilling Fluids). It should benoted that similar decreases are expected when rheology is measured atdifferent temperatures, such as 120° F.

In any aspect or embodiment described herein, the IEF of the presentdisclosure has a lower gel strength than a similarly formulated IEF witha maleated TOFA amine emulsifier. In certain embodiments, the IEF of thepresent disclosure has a gel strength that is about 10 to about 92%(e.g., about 25 to about 85% or about 50 to about 85%) lower than asimilarly formulated IEF comprising a maleated TOFA amine emulsifier at150° F. For example, in any aspect or embodiment described herein, theIEF of the present disclosure has a gel strength at 150° F. that isabout 10 to about 92%, about 10 to about 95%, about 10 to about 80%,about 10 to about 70%, about 10 to about 60%, about 10 to about 50%,about 10 to about 40%, about 10 to about 30%, about 20 to about 92%,about 20 to about 85%, about 20 to about 80%, about 20 to about 70%,about 20 to about 60%, about 20 to about 50%, about 20 to about 40%,about 30 to about 92%, about 30 to about 85%, about 30 to about 80%,about 30 to about 70%, about 30 to about 60%, about 30 to about 50%,about 40 to about 92%, about 40 to about 85%, about 40 to about 80%,about 40 to about 70%, about 40 to about 60%, about 50 to about 92%,about 50 to about 85%, about 50 to about 80%, about 50 to about 70%,about 60 to about 92%, 60 to about 85%, about 60 to about 80%, or about70 to about 92% lower than a similarly formulated IEF comprising amaleated TOFA amine emulsifier. It should be noted that one of ordinaryskill in the art would expect similar decreases in fluid gel strengthwhen rheology is measured at a different temperature, such as 120° F.

In any aspect or embodiment described herein, the IEF of the presentdisclosure has a lower yield stress (Tau0) than a similarly formulatedIEF with a maleated TOFA amine emulsifier. In certain embodiments, theIEF of the present disclosure has a yield stress that is about 10 toabout 92% lower than a similarly formulated IEF comprising a maleatedTOFA amine emulsifier at 150° F. This decrease is even observed inpresence of a high volume of low gravity solids as described herein(e.g. greater than about 10% V/V). For example, in any aspect orembodiment described herein, the IEF of the present disclosure has ayield stress at 150° F. that is about 10 to about 92%, about 10 to about85%, about 10 to about 80%, about 10 to about 70%, about 10 to about60%, about 10 to about 50%, about 10 to about 40%, about 10 to about30%, about 20 to about 92%, about 20 to about 85%, about 20 to about80%, about 20 to about 70%, about 20 to about 60%, about 20 to about50%, about 20 to about 40%, about 30 to about 92%, about 30 to about85%, about 30 to about 80%, about 30 to about 70%, about 30 to about60%, about 30 to about 50%, about 40 to about 92%, about 40 to about85%, about 40 to about 80%, about 40 to about 70%, about 40 to about60%, about 50 to about 92%, about 50 to about 85%, about 50 to about80%, about 50 to about 70%, about 60 to about 92%, 60 to about 85%,about 60 to about 80%, or about 70 to about 92% lower than a similarlyformulated IEF comprising a maleated TOFA amine emulsifier. It should benoted that similar decreases in yield stress is expected when rheologyis measured at a different temperature, such as 120° F. In any aspect orembodiment described herein, the IEF of the present disclosure has a gelstrength of about 10 to about 30 (e.g., about 10 to about 20, about 20to about 30, or about 15 to about 25).

In any aspect or embodiment described herein, the IEF of the presentdisclosure is used for gas drilling, oil drilling, or both.

Drilling Fluid

Another aspect of the present disclosure provides a drilling fluid thatcomprises the IEF of the present disclosure, the LGS tolerant emulsifierof the present disclosure, or both.

In another aspect or embodiment described herein, the drilling fluid ofthe present disclosure has a lower gel strength than a similarlyformulated drilling fluid comprising a maleated TOFA amine emulsifier,even in presence of a high volume or concentration of LGS (e.g. fromabout 4% to about 12% V/V of the drilling fluid).

In any aspect or embodiment described herein, the drilling fluid of thepresent disclosure has a lower rheology than a similarly formulateddrilling fluid comprising a maleated TOFA amine emulsifier, even inpresence of a high volume or concentration of LGS (e.g. from about 4% toabout 12% V/V of the drilling fluid).

In any aspect or embodiment described herein, the drilling fluid is usedfor gas or oil drilling.

Method of Drilling a Well

A further aspect of the disclosure provides a method of drilling a well.The method comprises drilling a well bore and circulating the drillingfluid of the any aspect or embodiment described herein through said wellbore when drilling the well bore.

Examples

The embodiments described above in addition to other embodiments can befurther understood regarding the following examples.

Rosin Acid (RA) Determination.

RA concentration was determined by titration. A modified Gliddenprocedure was utilized for RA concentration of about 15% or less, and amodified Wolff Method was utilized for RA concentration of about 15% orgreater. In particular, under the modified Wolff Method, 4.5-5.5 gramsof the low titer fatty acid material, 90-110 mL of methanol, and 5 mL ofmethyl sulfuric acid (20% in methanol) was added to an Erlenmeyer flask,and under the modified Glidden Method, 39-41 grams of the low titerfatty acid material, 140-160 mL of methanol, and 10 mL of methylsulfuric acid (20% in methanol) was added to an Erlenmeyer flask. If thesolution prepared under the modified or Wolff Method or the modifiedGlidden method is cloudy, toluene is added (up to 30 mL) until thesolution is clear. The flask of clear solution was connected to acondenser and refluxed for 20 minutes on a hotplate. The solution wasthen cooled. The rosin acid number was then determined through titrationof the cooled solution with 0.5N KOH in methanol on a 888 TitrandoAutotitrator (Metrohm, Riverview, Fla.).

Acid Number and Amine Value Determination.

Two grams of the low titer fatty acid material or amine material wasadded to a beaker. The low titer fatty acid material was dissolved inmethanol or a mixture of methanol and Toluene or isopropanol usingagitation and/or heat, as required for complete dissolution. The aminematerial was dissolved in 75 mL of isopropanol, using agitation and/orheat, as required for complete dissolution. Acid number was determinedvia titration with 0.5N KOH in methanol and the amine value wasdetermined via titration with 0.5 HCL in methanol on a 888 TitrandoAutotitrator (Metrohm, Riverview, Fla.).

Titer Point Determination.

Titer point of the low titer fatty acid material was determined via ASTMD1982-61. Briefly, the low titer fatty acid material was added to a testtube. A Thermometer and stirring wire was added to the test tube. Thetest tube assembly was placed in a frozen cold bath assembly. The stirwire completed approximately one-hundred 1-2″ up-and-down motions perminute. The temperature of the low titer fatty acid material was readevery 15 seconds until the temperature remained constant for 30 secondsor until a rise in temperature was observed. Stirring was discontinuedand any temperature rise was noted (exotherm portion). The titer pointis the highest temperature observed during the exotherm portion beforethe temperature began to decrease.

Gardner Color Index Determination.

The Gardner color index was determined according to ASTM D6166-12(2016).

Amount of Fatty Acid and Rosin Acid Determination.

The amount of fatty acid and rosin acid in the low titer fatty acidmaterial or components thereof was determined utilized the methoddescribed in ASTM D5974-15.

Preparation of an Exemplary Emulsifier of the Present Disclosure: C2-B®Based Emulsifier (i.e., a Maleated Amido Amine Based on C2-B®).

C2-B® was utilized as the low titer fatty acid material and is a lowtiter fatty acid material collected as the bottoms product during theproduction of low rosin (<5%) and low Gardner Color index (<7.0) talloil fatty acid (TOFA) from refinery columns during the distillation ofcrude tall oil (CTO). The acid number of the C2-B® can vary from about143-about 185 mg/g, but typically is about 155-about 174 mg/g. Amine HST(CAS #68910-05-4) was used as the amine material and is available as anamine stream procured from Dow Chemicals, the batch used had an aminevalue of approximately 750 mg/g.

Preparation of the maleated amido-amine reaction product:

-   -   1. About 350 grams (70% w/w) of the C2-B® (preheated) with an        acid number of 167.2 mg/gm was added into to the five neck round        bottom flask (1000 ml). Under stirring at 90 rpm, 150 grams (30%        w/w) of Amine HST was added, which gives an exotherm.    -   2. Once the temperature was stabilized, the reaction mixture was        heated to 135° C. over 35 minutes and then held at 135° C. for 1        hour.    -   3. The reaction mixture was ramped to 200° C. over 56 minutes        and held at 200° C. temperature for 2 hours.    -   4. After 2 hours, the reaction mixture was cooled to 100° C. The        amino-amine reaction product was transferred to a sample bottle.        The amine value of this C2-B® based amido-amine (i.e., the        amido-amine reaction product) was determined to be 133.9 mg/gm.    -   5. About 35.78 grams of the amido-amine reaction product was        heated to 65° C. in an aluminum can and 19.8 grams of a mineral        oil LVT 200 was added.    -   6. This reaction mixture was stirred while the temperature was        maintained at 65° C.    -   7. During stirring, 4.42 grams of molten Maleic Anhydride (MA)        was added dropwise. Since MA addition resulted in an exotherm,        the MA addition was controlled to ensure the temperature was        maintained at 85° C.    -   8. After the addition of all the MA, the reaction mixture was        stirred, while being held at 85° C., for 1 hour. The reaction        mixture was then cool to room temperature.    -   9. The resulting maleated C2-B amido-amine (i.e. the maleated        amido-amine reaction product) had an amine value of 30.29 mg/gm        and acid number of 52.59 mg/gm. This samples is labelled as        9160-57-11. Additional exemplary emulsifiers were prepared        utilizing similar methods and will now be described in greater        detail.

Exemplary and Comparative Emulsifiers utilized in the Examples are shownin Table 1. The Exemplary Emulsifiers (i.e., LGS tolerant emulsifier orMDTA emulsifier) of the disclosure were made with the indicated pure lowtiter distilled tall oil streams as the low titer fatty acid materialand are designated 9139-70-11 (C2-B®), 9160-57-11 (C2-B®), 9177-32-11(C2-B®), 9177-34-11 (C2-B®), 8998-75B-7 (Altapyne™ M28B) and 8998-75C-7(Altapyne™ 1430) in Table 1. The Exemplary Emulsifiers made with lowtiter distilled tall oil streams having acid numbers ranging from 147.9mg/g to 188.4 mg/g. Commercially available maleated TOFA amido-amineemulsifiers, which are the industry standard, were utilized asComparative Emulsifiers. The emulsifiers were tested at an effectiveconcentration of 10.7 ppb in the IEF. The formulations of thecompositions and reaction conditions are shown in Table 2.

The components of the fluids were mixed, then hot rolled for 16 hours at325° F. The fluids were then remixed on a multimixer for 5 minutes.Rheology and electrical stability (ES) were examined at 150° F. Fluidloss of the fluids was examined at 350° F., 500 psi differentials.

The rheology data of the invert emulsion fluids was measured at 150° F.and were modeled with the Herschel Buckley (HB) model. The HB modelparameters—Tau0 (yield stress), K (consistency index), & n (flowindex)—along with the Gel strength at 10 minutes, the ElectricalStability (ES), Fluid loss and Fann 35 rheometer readings from 600 to 3rpm dial readings are presented in Table 3 and 4 below. All fluidstested were stable after the hot roll (as observed from their textureand appropriate ES values), gave controlled fluid loss values at 350°F., and showed water in the filtrate.

The Gel Strengths with the maleated TOFA amido-amine emulsifiers werevery high at 58 units and 74 units. In comparison, the Gel strengths ofthe Exemplary Emulsifiers made with the low titer fatty acid material ofvarying acid numbers ranged from 15 to 21 units and 30-31 units. TheMaleated TOFA amido-amine-1, 9139-70-11, 9160-57-11, 9177-32-11, and9177-34-11 were analyzed with a different batch of REV DUST® than theMaleated TOFA amido-amine-2, 8998-75B-7, and 8998-75C-7. Thus, while8998-75B-7 and 8998-75C-7 have higher Gel strengths than the otherExemplary Emulsifiers, this appears to be a result of the REV DUST batchutilized as the Maleated TOFA amido-amine-2, which is the same productas the Maleated TOFA amido-amine-1, demonstrated a higher Gel strength.Thus, a decrease in Gel strength was observed in each of the ExemplaryEmulsifiers as compared to the concomitantly analyzed comparativeexample.

Similarly, the Tau0 (yield stress) from the HB model were in the rangeof 5-10 for the Exemplary Emulsifier made with low titer fatty acidmaterial. The commercial available maleated TOFA amine emulsifierdemonstrated a very high Tau0 at 39.7 and 59.3.

The appreciable gels are required for suspension whereas the lowrheology will help to maintain low ECD (in this case in the presence ofhigh LGS @ 100 ppb).

FIGS. 1 and 2 present the rheology data of shear stress versus shearrate for exemplary fluids of the present disclosure, as well ascomparative fluids. The rheograms of FIGS. 1 and 2 demonstrate that thefluids of the present disclosure formulated with the emulsifier of thepresent disclosure has low rheology, as compared to the commerciallyavailable maleated TOFA amine emulsifier. Thus, the fluids of thepresent disclosure comprising the emulsifier of the present disclosurewere surprisingly able to tolerate the presence of 100 ppb LGS.

A low rheology typically delivers a low ECD, while drilling oil and gaswells. A low ECD generally leads to lower induced fluid losses to theformation. Since invert emulsion fluids are expensive, lower inducedfluid losses to the formation are desired. A high concentration of lowgravity solids (drilled solids) in the fluid typically increases theoverall rheology of the fluid thereby leading to higher ECD, andtherefore, higher induced fluid losses to the formation. A low rheologyshould be coupled with appreciable gels, since when drilling stops andfluid is in a static condition, the gels help to maintain the barite anddrilled solids in suspension. A fluid with low gels can lead to baritesag and poor hole cleaning, both of which can lead to loss of precioustime at the rig when drilling oil and gas wells.

TABLE 1 Emulsifiers used to test against low gravity solids tolerance inthe IEF AN of MA % low titer fatty Bisamide Product in 100% active HoldTemp acid material LTFAM AMINE Emulsifier** of Amide Emulsifier % Active(mg/g) %* HST % (undiluted) Reaction Maleated 66.7 TOFA amido- amine - 19139-70-11 66.7 163.0 70 30 11 200 9160-57-11 66.7 167.2 70 30 11 2009177-32-11 66.7 157.8 70 30 11 200 9177-34-11 66.7 147.9 70 30 11 2008998-75B-7 66.7 188.4 70 30 7 200 8998-75C-7 66.7 181.4 70 30 7 200Maleated 66.7 TOFA amido- amine - 2 *LTFAM—low titer fatty acidmaterial. **MA—maleic anhydride

TABLE 2 Inverted Emulsion Fluid with 100 ppb REV DUST ® formulation Mixthe additives for the given time. Hot roll at 325° F. for 16 hours Afterhot roll, remix on multimixer 5 minutes. Check rheology and ES at 150°F. Determine HTHP FL at 350° F., 500 psi differentials Volume WeightTime Mud S.G (ml) (grams) (minutes) ESCAID 110 mineral oil 0.80 156.45125.16 Emulsifier 0.96 16.67 16.00 1.0 Lime - Alkalinity Control agent2.24 1.34 3.00 1.0 Polymer fluid loss 1.03 2.91 3.00 10.0 additive basedon styrene methacrylate copolymer Brine with CaCl₂ (300K WPS) 1.29 67.0586.16 10.0 Dimer fatty acid viscosifier 0.96 3.13 3.00 5.0 REV DUST ®simulate drilled 2.70 37.04 100.00 5.0 low gravity solids Barite,weighting agent 4.20 65.42 274.77 10.0 Total weight in grams 611.1 Totalvolume in ml 350.0 Mud weight in ppg 14.57

TABLE 3 Fluid loss, Herschel Buckley parameters, Gel Strength andElectrical Stability of invert emulsion fluids Gel 10 min ES in mV Tau0K N Fluid loss Emulsifier Effective @ 150° F. @ 15° F. @ 150° F. @ 1500°F. @ 150° F. @ 350° F. Maleated TOFA 10.7 58 277 39.7 1.181 0.842 7.2(2.4) amido-amine (AN = 192 mg/g) 9139-70-11 10.7 21 144 9.3 0.723 0.83711.6 (DNM) (LTFAM* AN = 163 mg/g) 9160-57-11 10.7 18 144 8.0 0.477 0.88810.0 (3.6) (LTFAM* AN = 167.2 mg/g) 9177-32-11 10.7 18 147 6.7 0.5720.871 8.8 (2.4) (LTFAM* AN = 157.8 mg/g) 9177-34-11 10.7 15 141 5.70.490 0.895 8.0 (2.0) (LTFAM* AN = 147.9 mg/g) 8998-75B-7 10.7 30 27017.9 0.722 0.855 7.2 (LTFAM* AN = 188.35 mg/g) 8998-75C-7 10.7 31 17712.1 0.727 0.862 7.2 (LTFAM* AN = 181.39 mg/g) Maleated TOFA 10.7 74 30059.3 1.859 0.800 4.0 amido-amine - 2 (AN = 192 mg/g) *LTFAM—low titerfatty acid material

TABLE 4 Rheology of inverted emulsion fluids at 600 rpm to 3 rpm dialreadings Rotations per minute at 150° F. Effective 600 300 200 100 6 3Emulsifier concentration rpm rpm rpm rpm rpm rpm Maleated TOFA 10.7298.2 183.8 142.1 96.8 45.0 42.7 amido amine (AN = 192 mg/g) 9139-70-1110.7 162.6 95.1 70.4 43.5 12.6 11.2 (LTFAM* AN = 163 mg/g) 9160-57-1110.7 147.9 83.6 60.7 36.5 10.3 9.3 (LTFAM* AN = 167.2 mg/g) 9177-32-1110.7 156.7 88.7 64.3 38.2 9.4 8.2 (LTFAM* AN = 157.8 mg/g) 9177-34-1110.7 155.7 86.4 61.8 35.9 8.2 7.0 (LTFAM* AN = 147.9 mg/g) 8998-75B-710.7 190 111 86.1 55.7 20.8 19.9 (LTFAM* AN = 188.35 mg/g) 8998-75C-710.7 193.1 111.1 82.1 51.2 15.4 13.8 (LTFAM* AN = 181.39 mg/g) MaleatedTOFA 10.7 368.9** 237.3 187.6 133.6 66.1 64.7 amido-amine - 2 (AN = 192mg/g) *LTFAM—low titer fatty acid material. **Estimated via the HBmodel.

While preferred embodiments of the present disclosure have been shownand described herein, it will be understood that such embodiments areprovided by way of example only. Numerous variations, changes andsubstitutions will occur to those skilled in the art without departingfrom the spirit of the present disclosure. Accordingly, it is intendedthat the appended claims cover all such variations as fall within thespirit and scope of the invention. Furthermore, the system may compriseat least one device for charging and/or discharging the system or aplurality of devices for charging and/or discharging the system.

The contents of all references, patents, pending patent applications andpublished patents, cited throughout this application are herebyexpressly incorporated by reference.

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, many equivalents to the specificembodiments of the present disclosure described herein. Such equivalentsare intended to be encompassed by the following claims. It is understoodthat the detailed examples and embodiments described herein are given byway of example for illustrative purposes only, and are in no wayconsidered to be limiting to the invention. Various modifications orchanges in light thereof will be suggested to persons skilled in the artand are included within the spirit and purview of this application andare considered within the scope of the appended claims. For example, therelative quantities of the ingredients may be varied to optimize thedesired effects, additional ingredients may be added, and/or similaringredients may be substituted for one or more of the ingredientsdescribed. Additional advantageous features and functionalitiesassociated with the systems, methods, and processes of the presentdisclosure will be apparent from the appended claims. Moreover, thoseskilled in the art will recognize, or be able to ascertain using no morethan routine experimentation, many equivalents to the specificembodiments of the present disclosure. Such equivalents are intended tobe encompassed by the following claims.

What is claimed is:
 1. A low gravity solid (LGS) tolerant emulsifiercomprising a maleated amido-amine reaction product produced by: reacting(i) a fatty acid material and (ii) an amine material to produce anamido-amine reaction product; and reacting the amido-amine reactionproduct with maleic anhydride to produce the maleated-amido-aminereaction product, wherein the fatty acid material includes at least oneof: an acid number ranging from about 143 to about 200 mg/g; a fattyacid concentration of about 34% to about 89%; a rosin acid concentrationof about 11% to about 50%; a titer point of less than about 14° C.; aPAN rosin acid concentration of less than or equal to about 50%; heaviespresent in an amount of less than or equal to about 40% of the fattyacid material, wherein the heavies are fatty acids or rosin acids thathave a boiling point higher than monomer fatty and rosin acids formedduring a distillation process; a Gardner color index in a range fromabout 4.0 to about 17.0, wherein the Gardner color index is determinedwith ASTM D6166-12 (2016); one or more of: C18 type fatty acids ispresent in an amount of about 25 to about 89%, C20 type fatty acids ispresent in an amount of less than or equal to about 34%, and C16 typefatty acids is present in an amount of no greater than about 5%; or acombination thereof.
 2. The emulsifier of claim 1, wherein at least oneof: the fatty acid material is present in an amount of about 55 wt. % toabout 95 wt. % of the amido-amine reaction product; the amine materialis present in an amount of about 5 wt. % to about 45 wt. % of theamido-amine reaction product; the maleic anhydride is present in anamount of about 1 wt. % to about 20 wt. % of the maleated amido-aminereaction product or the emulsifier; or a combination thereof.
 3. Theemulsifier of claim 1, wherein the fatty acid material has an acidnumber ranging from about 155 to about 174 mg/g.
 4. The emulsifier ofclaim 1, wherein the fatty acid material includes at least one of: aside stream from the oil collected as the bottoms product during theproduction of low rosin (<5%) and low Gardner Color index (<7.0) talloil fatty acid (TOFA) from refinery columns during the distillation ofcrude tall oil (CTO); a mixture of the side stream and at least one ofdistilled tall oil, TOFA, rosin, or a combination thereof; a productstream of the CTO refining process; a mixture of TOFA and distilled talloil; a mixture of distilled tall oil and rosin; a mixture of TOFA androsin; a disproportionated tall oil, a mixture of disproportionated talloil and rosin, a mixture of disproportionated tall oil and TOFA, amixture of disproportionated tall oil and distilled tall oil, or acombination thereof; or a combination thereof.
 5. The emulsifier ofclaim 1, wherein the amine material has an amine value of about 700 toabout 1300 mg/g.
 6. The emulsifier of claim 1, wherein the aminematerial has an amine value of about 700 to about 900 mg/g.
 7. Theemulsifier of claim 1, wherein the amine material is or includes adistillation residuum bottom composition of a reaction product ofmonoethanolamine and ammonia in which piperazine distillate product hasbeen recovered.
 8. The emulsifier of claim 1, wherein the amine materialincludes at least one of: diethylenetriamine (DETA),hydroxyethyldiethylenetriamine (HEDETA), 2-piperazinoethanol,triethylenetetramine (TETA), Tetraethylenepentamine (TEPA),pentaethylene hexamine (PEHA) heptaethyleneoctamine (HEOA),hexaethyleneheptamine (HEHA)amine HST, amine DCT, aminoethylpiperazine(AEP), dimethylaminopropylamine (DMAPA), aminoethylethanolamine (AEEA),diethanolamine (DEA), triethanolamine (TEA), monoethanolamine, orcombinations thereof.
 9. The emulsifier of claim 1, wherein theamido-amine reaction product includes at least one of bis-amidoamines,alkanolamides, di-ester alcohol amine, ester alcohol amine, di-esteramine, ester amido amines, amido amine alcohols, amides of the hydroxypiperazine, amide imidazoline, ester imidazoline, amine imidazoline,alkanol imidazoline or combinations thereof.
 10. An invert emulsionfluid (IEF) comprising the emulsifier of claim 1, and at least one of: anon-aqueous continuous phase, a discontinuous hygroscopic phase likebrine, an additive, or a combination thereof.
 11. The IEF of claim 10,further comprising greater than about 10% V/V of low gravity solidshaving a specific gravity of about 2.0 to about 3.0.
 12. The IEF ofclaim 10, further comprising about 4 to about 12% V/V of low gravitysolids having a specific gravity of about 2.0 to about 3.0.
 13. The IEFof claim 10, wherein the IEF has a high temperature, high pressure fluidloss of about 1 to about 20 mL at 350° F.
 14. The IEF of claim 10,wherein the IEF has a lower rheology than an IEF comprising a maleatedtall oil fatty acid (TOFA) amine emulsifier.
 15. The IEF of claim 10,wherein the IEF has at least one of: a rheology that is about 10-about92% lower that a similarly formulated IEF comprising a maleated tall oilfatty acid (TOFA) amine emulsifier as determined by taking readings from600 rpm to 3 rpm at 150° F.; a gel strength that is about 10 to about92% lower than a similarly formulated IEF with a maleated TOFA amineemulsifier at 150° F.; a yield stress (Tau0) that is less than asimilarly formulated IEF with a maleated TOFA when measured at 150° F.;or a combination thereof.
 16. The IEF of claim 10, wherein the IEF isused for gas drilling and/or oil drilling.
 17. The IEF of claim 10,wherein the additive includes at least one of: a rheology modifier,emulsifier, wetting agent, viscosifier, lime, salt, fluid loss additive,lost circulation material, weighting agent, or a combination thereof.18. A drilling fluid comprising the IEF of claim
 10. 19. A method ofdrilling a well, the method comprising drilling a well bore andcirculating the drilling fluid of claim 18 through said well bore whendrilling the well bore.
 20. The invert emulsion fluid (IEF) of claim 10,wherein the discontinuous hygroscopic phase is brine.
 21. A method ofmaking an emulsifier, the method comprising: reacting (i) a fatty acidmaterial comprising and (ii) an amine material to produce an amido-aminereaction product; and reacting the amido-amine reaction product withmaleic anhydride to produce a maleated amido-amine reaction product,wherein the fatty acid material includes at least one of: an acid numberranging from about 143 to about 200 mg/g; a fatty acid concentration ofabout 34% to about 89%; a rosin acid concentration of about 11% to about50%; a titer point of less than about 14° C.; a PAN rosin acidconcentration of less than or equal to about 50%; heavies present in anamount of less than or equal to about 40% of the fatty acid material,wherein the heavies are fatty acids or rosin acids that have a boilingpoint higher than monomer fatty and rosin acids formed during adistillation process; a Gardner color index in a range from about 4.0 toabout 17.0, wherein the Gardner color index is determined with ASTMD6166-12 (2016); or a combination thereof.